Electronic Supporting Information

Metal-involving Chalcogen Bond. The Case of Platinum(II) Interaction with

Se/Te-based -Hole Donors

Anton V. Rozhkov,1 Eugenе A. Katlenok,1 Margarita V. Zhmykhova,1 Alexander Yu. Ivanov1,

Maxim L. Kuznetsov,2 Nadezhda A. Bokach,1 Vadim Yu. Kukushkin*1,3

1Institute of Chemistry, Saint Petersburg State University, Universitetskaya Nab. 7/9, 199034 Saint

Petersburg, Russian Federation; e-mail: v.kukushkin@spbu.ru

2Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco

Pais, 1049–001 Lisboa, Portugal; e-mail: max@mail.ist.utl.pt

3Laboratory of Crystal Engineering of Functional Materials, South Ural State University, 76,

Lenin Av., Chelyabinsk, 454080 Russian Federation

1
Contents

1. EXPERIMENTAL SECTION 3

1.1 Starting materials 3

1.2 ANALYTICAL METHODS 3

1.2.1 NMR spectroscopy 3
1.2.2 X-ray structure determinations 3
1.2.3 Isothermal titration calorimetry 3

2. CRYSTAL DATA AND STRUCTURE REFINEMENT 4

2.1 Crystal growth 4

2.2 Structural motifs of the XRD structures 5

3. HIRSHFELD SURFACE ANALYSIS 9

3.1 Hirshfeld surface analysis – general setup 9

3.2 Results of Hirshfeld surface analysis 10

4. COMPUTATIONAL DETAILS 13

4.1 Computational models 15

4.1 QTAIM and IGMH analyses 16

4.2 NBO and CDF analyses 21

4.3 Interaction energies and SAPT-based decomposition 27

4.4 Supermolecular approach 29

4.5 Cartesian coordinates for the studied molecules 32

4.5.1 Optimized geometries 32
4.5.2 Optimized geometries in CHCl3 solution 49
4.5.3 X-ray geometries 53

5. METAL-INVOLVING CHALCOGEN BONDING IN SOLUTIONS 76

SUPPLEMENTARY INFORMATION REFERENCES 81

2
1. Experimental section
1.1 Starting materials
All solvents were obtained were obtained from commercial sources and were used without further
purification. ITC solvents were degassed prior used. Pt(ppy)acac,1 Pt(ppy)tmhd,2 (4-NC5F4)2Se3
and (4-NC5F4)2Te3 were synthesized via previously published procedures.

1.2 Analytical methods

1.2.1 NMR spectroscopy

NMR spectra were recorded on a Bruker AVANCE III 400 spectrometer at ambient temperature

in CDCl3 at 400 MHz (1H), 101 MHz (13C), 376 MHz (19F), 76 MHz (77Se), 126 MHz (125Te) and

86 MHz (195Pt).Chemical shifts are given in δ (ppm) values referenced to the residual signals of

CDCl3. To determine the stoichiometry and association constant corresponding to the interactions

between 2 and (4-NC5F4)2Te, 195Pt and 125Te NMR titration were carried out using solutions that

contained a constant concentration of 2 (34 mM) while varying the concentrations of (4-NC5F4)2Te

and a constant concentration of (4-NC5F4)2Te (32 mM) while varying the concentrations of 2. By

means of standard non-linear curve-fitting using the supramolecular.org web applet4-5, the

association constant corresponding to the interaction between 2 and (4-NC5F4)2Te was calculated.

Fitting data available via links http://app.supramolecular.org/bindfit/view/82dbe7ec-d267-4551-

aafe-14a50f7b25b0 (195Pt titration) and http://app.supramolecular.org/bindfit/view/1035cdad-

7da4-4b3d-9d4f-8dba3e3e94dc (125Te titration).

1.2.2 X-ray structure determinations

Suitable single crystals of 1·½(4-NC5F4)2Se were studied on a Rigaku XtaLAB Synergy-S
diffractometer (Cu Kα (λ = 1.54184), 1·½(4-NC5F4)2Te on SuperNova, Dual, Cu at home/near,
Atlas diffractometer (Cu Kα (λ = 1.54184), 2·(4-NC5F4)2Te on Xcalibur, Eos diffractometer (Mo
Kα (λ = 0.71073). The crystals were kept at 100 K during data collection. The CrysAlisPro6
software package was used for cell refinements and data reductions. All structures were solved by
direct methods using SHELXT7 and refined against F2 using SHELXL8. All non-hydrogen atoms
were refined with individual anisotropic displacement parameters. The hydrogen atoms in all
3
structures were placed in ideal calculated positions and refined as riding atoms with relative
isotropic displacement parameters.
1.2.3 Isothermal titration calorimetry
ITC experiments were conducted at 25 °C using the NANO ITC 2G calorimeter (TA Instruments,
USA). The temperature was set to 25С, deviation from this value did not exceed 0.0005С. The
measurement cell was filled with 2 solution in CHCl3 (22.5 mM). The syringe was filled with a
176.55 mM solution in CHCl3 of the (4-NC5F4)2Te. The time between each injection, 9.98 µl each,
was set to 600 seconds. The total number of injections was 24. Stirring speed was set to 250 rpm
to ensure a good mixing in the reaction vessel. The experiments are corrected for the energy of
dilution of the titrant, calculated based on a blank measurement.

4
2. Crystal data and structure refinement

Table S1. Crystal data and structure refinement for 1·½(4-NC5F4)2Se, 1·½(4-NC5F4)2Te, and
2·(4-NC5F4)2Te

Identification code 1·½(4-NC5F4)2Se 1·½(4-NC5F4)2Te 2·(4-NC5F4)2Te

Empirical formula C42H30F8N4O4Pt2Se C42H30F8N4O4Pt2Te C32H27F8N3O2PtTe
Formula weight 1275.84 1324.48 960.25
Temperature/K 100(2) 100.00(10) 100.5(8)
Crystal system triclinic triclinic triclinic
Space group P-1 P-1 P-1
a/Å 10.8219(2) 10.7074(4) 9.9566(2)
b/Å 13.7931(3) 13.7344(5) 10.9040(3)
c/Å 13.8529(3) 14.0458(6) 14.9936(3)
α/° 80.383(2) 80.713(3) 86.291(2)
β/° 86.5250(10) 73.131(4) 89.179(2)
γ/° 72.040(2) 85.701(3) 78.497(2)
Volume/Å3 1939.30(7) 1949.92(14) 1591.77(6)
Z 2 2 2
ρcalcg/cm3 2.185 2.256 2.003
μ/mm-1 15.159 19.794 5.388
F(000) 1208.0 1244.0 916.0
Crystal size/mm3 0.2 × 0.2 × 0.15 0.12 × 0.1 × 0.08 0.15 × 0.14 × 0.1
Radiation Cu Kα (λ = 1.54184) Cu Kα (λ = 1.54184) Mo Kα (λ = 0.71073)
2Θ range for data
6.472 to 139.998 6.524 to 139.998 4.98 to 59.222
collection/°
-13 ≤ h ≤ 13, -16 ≤ k ≤ -13 ≤ h ≤ 13, -16 ≤ k -12 ≤ h ≤ 13, -14 ≤ k ≤
Index ranges
16, -16 ≤ l ≤ 16 ≤ 16, -17 ≤ l ≤ 16 14, -19 ≤ l ≤ 20
Reflections collected 77016 34201 28434
7336 [Rint = 0.0706, 7372 [Rint = 0.0743, 7734 [Rint = 0.0331,
Independent reflections
Rsigma = 0.0261] Rsigma = 0.0482] Rsigma = 0.0340]
Data/restraints/parameters 7336/0/554 7372/0/512 7734/0/430
Goodness-of-fit on F 2 1.104 1.035 1.052
R1 = 0.0296, wR2 = R1 = 0.0309, wR2 = R1 = 0.0263, wR2 =
Final R indexes [I>=2σ (I)]
0.0816 0.0716 0.0523
R1 = 0.0304, wR2 = R1 = 0.0402, wR2 = R1 = 0.0314, wR2 =
Final R indexes [all data]
0.0824 0.0766 0.0544
Largest diff. peak/hole / e Å-
3 2.23/-1.79 1.67/-1.64 1.24/-0.86
CCDC Nos 2090272 2090273 2090274

2.1 Crystal growth

Single crystals of for 1·½(4-NC5F4)2Se, 1·½(4-NC5F4)2Te, 2·2/3(4-NC5F4)2Se, and 2·(4-
NC5F4)2Te were obtained by slow evaporation at RT of a chloroform solution (4 mL) of a

5
 mixture of the corresponding platinum diketonate complex and (4-NC5F4)2Ch taken in 1:1
molar ratio. Crystals suitable for XRD were released after 3–4 d.

2.2 Structural motifs of the XRD structures

III

N Pt
I O
F O

Me

N F Te Me

II Me
O N
Pt
O
Me

Me
O
Pt
N O
Me

Figure S1. View of four-component associate in the structure of 1·½(4-NC5F4)2Te with the

destignation of two different molecules of 1 (left panel) and its schematic representation with

fragment numbering (right panel). The same fragment numbering scheme was applied in the

theoretical part.

6
Figure S2. Molecular environment of two independent molecules of 1 in the structure of 1·½(4-

NC5F4)2Se. 1A (left panel) exhibits the Se···Pt and Pt···Pt short contacts (dotted lines), while 1B

displays the Se···C short contacts (dotted line).

Figure S3. Molecular environment of two independent molecules of 1 in the structure of 1·½(4-

NC5F4)2Te exemplified by the 12{(4-NC5F4)2Te}2 tetramers1A (left panel) exhibits the Te···Pt

and Pt···Pt short contacts (dotted line) and 1B displays the Te···C short contacts (dotted line).

7
Figure S4. A fragment of the crystal packing of 1·½(4-NC5F4)2Se illustrating the infinity chain

of alternating 1A2 and 1B2 dimers linked by (4-NC5F4)2Se functioning as a bifunctional ChB

donor.

Figure S5. A fragment of the crystal packing of 1·½(4-NC5F4)2Se illustrating the assembling of

2D layer.

8
Figure S6. A fragment of the crystal packing of 1·½(4-NC5F4)2Te showing an infinite chain of

alternating 1A2 and 1B2 dimers linked by (4-NC5F4)2Te; the latter acts as a bifunctional ChB

donor.

Figure S7. A fragment of the crystal packing of 1·½(4-NC5F4)2Te showing 2D-layers.

The infinite chains of alternating 1A2 and 1B2 dimers (linked by (4-NC5F4)2Ch functioning

as bifunctional ChB donors) are assembled via Ch···Pt, Ch···C, Pt···Pt and π-stacking interactions

(Figures S4 and S6). Withing these chains, 1A and 1B are additionally linked by hydrogen bonds

(HB) between the CHppy of 1A and the ppy ring of 1B. Molecules of 1B form intermolecular HB

between the CH3 and =Oacac. The chains are aggregated into 2D-layers via, on the one hand, π-

stacking between the {NC5F4} fragments and, on the other hands, LP–(π-hole) interaction between

the F atom and an arene ring of two neighboring (4-NC5F4)2Ch. Additional contacts are

represented by π-stacking between the {Pt(ppy)} moieties of 1B from two neighboring chains, and

HB between CHppy and F centers of the {NC5F4} moiety (Figures S5 and S7). The layers are

connected through HB between CHppy of 1 and F atoms of {NC5F4}.

9
Figure S8. Molecular structure of 2·2/3(4-NC5F4)2Se. Only two out of three independent molecules

of 2 and one out of two independent molecules of (4-NC5F4)2Se are shown for simplicity.

3. Hirshfeld surface analysis

3.1 Hirshfeld surface analysis – general setup
HSA was carried out using the CrystalExplorer 17.5 software.9-10 The normalized contact
distances, dnorm, based on RvdW, were mapped on the Hirshfeld surface. In the color scale, the
negative values of dnorm are visualized by red color indicating the contacts shorter than the sum of
RvdW. The values represented in white denote the intermolecular distances close to the vdW
contacts with dnorm equal to zero. In turn, the contacts longer than RvdW with positive dnorm values
are colored in blue.

10
 3.2 Results of Hirshfeld surface analysis

Figure S9. Hirshfeld surfaces mapped with dnorm over the range –0.29 (red) to 1.36 (blue) for 1A

(top left panel) and 1B (top right panel), and (4-NC5F4)2Te (bottom panel) in the XRD structure

of 1·½(4-NC5F4)2Te.

11
Figure S10. Hirshfeld surfaces mapped with dnorm over the range–0.20 (red) to 1.38 (blue) for 1A

(top left panel) and 1B (top right panel), and (4-NC5F4)2Se (bottom panel) in the XRD structure

of 1·½(4-NC5F4)2Se.

12
Figure S11. The Hirshfeld surface of 2 in the XRD structure of 2·(4-NC5F4)2Te from the side of

Te···Pt contact mapped with dnorm over the range –0.38 (red) to 1.64 (blue) (left panel) and shape

index S, mapped from –1.0 (concave hollows; red) –1 0.0 (minimal saddle; green)  +1.0

(convex bumps; blue) (right panel).

13
 Table S2. Results of HSA for 1·½(4-NC5F4)2Se, 1·½(4-NC5F4)2Te, and 2·(4-NC5F4)2Te.

Contributions of various intermolecular contacts to the molecular Hirshfeld

molecule
surface
1·½(4-NC5F4)2Se
H···H 38.3%, H···C 24.3%, H···F 16.8%, C···C 5.1%, C···O 4.3%, H···N
1A
2.6%, N···O 1.6%, Pt···Pt 1.3%, O···F 1.2%, C···Se 1.1%, Pt···Se 0.6%
H···H 36.4%, H···C 20.4%, H···F 19.5%, C···C 5.1%, H···O 4.8%, H···N
1B
3.2%, C···O 2.1%, Pt···H 1.8%, C···F 1.5%, H···Se 1.8%, C···Se 0.5%
F···H 49.8%, F···C 7.9%, C···N 6.9, F···F 6.4%, H···N 4.9%, C···C 4.3%,
(4-NC5F4)2Se H···Se 3.9%, C···O 3.6%, F···O 2.5%, C···Se 2.2%, Pt···C 1.9%, H···C
1.2%, N···N 1.2%, N···Se 1.0%, Se···Pt 0.8%
1·½(4-NC5F4)2Te
H···H 38.4%, H···C 24.0%, H···F 16.6%, C···C 5.5%, C···O 4.4%, H···N
1A
2.5%, N···O 1.6%, O···F 1.3%, Pt···Pt 1.1%, C···Te 1.0%, Pt···Te 0.9%
H···H 36.0%, H···C 21.0%, H···F 19.4%, H···O 5.0%, C···C 4.3%, H···N
1B 2.9%, C···O 2.1%, C···F 2.0%, Pt···H 1.8%, H···Te 1.7%, Pt···C 1.0%,
C···Te 0.7%
F···H 47.9%, F···C 8.2%, C···N 6.9, F···F 6.8%, H···N 4.8%, H···Te 4.5%,
(4-NC5F4)2Te C···C 4.4%, C···O 3.2%, F···O 2.6%, C···Te 2.5%, H···C 1.7%, Pt···C
1.7%, N···Te 1.1%, Te···Pt 1.0%
2·½(4-NC5F4)2Te
H···H 35.0%, H···F 30.9%, H···C 8.8%, C···C 5.0%, H···N 4.9%, C···F
2 3.8%, H···O 3.2%, C···N 2.4%, C···Pt 1.5%, C···Te 1.4%, Pt···Te 0.9%,
H···Te 0.9%
F···H 52.5%, F···C 9.7%, H···N 9.3, C···H 8.9%, C···C 4.0%, H···Te 3.2%,
(4-NC5F4)2Te F···F 3.0%, Te···O 1.7%, F···N 1.7%, Te···F 1.5%, Te···Pt 1.4%, C···N
1.1%, Te···C 1.0%

4. Computational details

Wave function calculations for the QTAIM, IGMH, EDD and NBO analyses were carried

out using the crystallographic coordinates at the DFT PBE011-12 level of theory with the atom-

pairwise dispersion correction and the Becke–Johnson damping scheme D3BJ13-14 with the help

of the ORCA package (version 4.2.1).15-17 Zero-order regular approximation (ZORA)18 was

employed to account for relativistic effects. The ZORA-def2-TZVP(-f)18 basis sets were used for

the H, C, N, F, O, and Se atoms while the SARC-ZORA-TZVP basis sets were used for the Pt and

Te atoms.19 Combination of the “resolution of identity” and the “chain of spheres exchange”
14
algorithms (RIJCOSX)20 in conjunction with the auxiliary basis sets SARC/J were used.21 The

SCF calculations were tightly converged (TightSCF). Numerical integrations during all DFT

calculations were done on a dense grid “ORCA grid7 and gridx8”, while “ORCA specialgridintacc

9” was used on the heavy atoms Pt, Se and Te.

The QTAIM and IGMH calculations were carried out using the Multiwfn 3.8 software.22-
24 The molecular electrostatic potential (MEP) was calculated on the 0.001 a.u. isosurface of

electron density. MEP was visualized using the Multiwfn software and the VMD program.25 The

SAPT calculations at the SAPT0 level were performed with the recommended basis sets jun-cc-

pVDZ and aug-cc-pvtz-pp for Pt and Te, respectively, for the bimolecular structures bearing

complex 1, 2 and (4-NC5F4)2Ch) at the crystallographic geometries using the Psi4 package.26 The

natural bond orbital analysis27 was performed using the NBO 7.0 program.28 The Charge

Displacement Function analysis (CDF) was carried out according to the methodology described

in refs.29-31 using the Multiwfn software.

All single point calculations for the estimates of interaction energies at the supermolecular

approach as well as geometry optimizations were carried out at the DFT PBE0-D3BJ level of

theory with the help of Gaussian16 program package.32 For geometry optimization, the DZP basis

set was used from the EMSL Basis Set Exchange Library.33 For single point calculations based on

X-ray or optimized geometries, the DZP-DKH basis set and the Douglas–Kroll–Hess second-order

scalar relativistic method (DKH)33-34 were applied. Ultrafine integration grid was applied for

numerical integrations. Basis set superposition error (BSSE) was estimated using the counterpoise

method35 at the PBE0-D3BJ/DZP-DKH level. The BSSE corrected Eint values for the formation

of the A···B bond were calculated as

Eint(A···B) = E(A···B)DZP-DKH – E(A)DZP-DKH – E(B)DZP-DKH + BSSE DZP-DKH

where E(A–B)DZP-DKH, E(A)DZP-DKH and E(B)DZP-DKH are total energies of A···B, A and B

and BSSEDZP-DKH is BSSE correction, all obtained at the PBE0-D3BJ/DZP-DKH//DZP level (see

15
section Supermolecular approach for the details of the interaction and binding energy calculations

and for the computational models).

The Gibbs free energies of the 2·(4-NC5F4)2Te formation in CHCl3 solution from 2 and (4-
NC5F4)2Te (Gs) were calculated using eqs. 1 and 2
Gs = Hs – TSs + BSSEDZP-DKH (1)
Hs = Es,DZP-DKH – Eg,DZP + Hg,DZP (2)
where Es,DZP-DKH is the total energy of reaction in solution calculated at the SMD-PBE0-
D3BJ/DZP-DKH level with CHCl3 as solvent, Eg,DZP and Hg,DZP are the total energy and enthalpy
of reaction in gas phase calculated at the PBE0-D3BJ/DZP level.
The entropic term in solution (Ss) was calculated according to the procedure described by
Wertz36 and Cooper and Ziegler37 using eqs. 3–6:
ΔS1 = R ln(Vsm,liq/Vm,gas) (3)
ΔS2 = R ln(V°m/Vsm,liq) (4)
α = [S°,sliq – (S°,sgas + S1)]/[S°,sgas + S1] (5)
Ss = Sg + Ssol = Sg + [S1 + α(Sg + S1) + S2] =
Sg + [(–5.00 cal/mol•K) – 0.19(Sg – 11.19 cal/mol•K)] (6)
where Sg is the gas-phase entropy of solute, ΔSsol is the solvation entropy, S°,sliq, S°,sgas, and Vsm,liq
is the standard entropies and molar volume of CH2Cl2 in liquid or gas phases, Vm,gas is the molar
volume of the ideal gas at 25 °C (22414 mL/mol), and V°m is the molar volume of the solution
corresponding to the standard conditions (1000 mL/mol).

4.1 Computational models

Wave-function calculations for the QTAIM, IGMH, EDD and NBO analyses were carried

out at the DFT PBE0-D3BJ/ZORA-def2-TZVP level of theory for the clusters (a) and (b) (Figure

S12a. c) using crystallographic coordinates. To calculate the contribution of the Pt–Pt interaction

to the total energy, we used the cluster (b) (Figure S12b).

16
 Figure S12. Clusters used in calculations.

4.1 QTAIM and IGMH analyses

The QTAIM molecular graph (Figure S3) revealed the presence of bonds critical points

(BCP) and bond paths for all discussed types of contacts except the Pt···C1D one. The nature of

ChB can be characterized by the value of electron density (b), Laplacian (2b) and total energy

density (Hb) at the BCP. It is well‐known that the b at the BCPs provides valuable information

regarding the strength of the noncovalent interactions involved in adduct formation. As can be

seen from the QTAIM results in Table S4, the b and its 2b values at the BCP of the σ-

hole[Ch]···dz2[Pt] contact is generally larger than for the σ-hole[Ch]···π[C] contact that indicates

that the first contact is stronger. It should be highlighted that σ-hole[Ch]···dz2[Pt] interaction is

stronger in 2·(4-NC5F4)2Te compared to 1·½(4-NC5F4)2Ch. The π–π interactions between the

perfluorpyridyl and diketonate fragments in 1·½(4-NC5F4)2Ch and between the perfluorpyridyl

and 2-phenylpyridine in 2·(4-NC5F4)2Te are characterized by the presence of a cage critical point

(CCP).38-39 The increase of the ρb values (Figure S14, Table S3) in these BCP and CCP from Ch

17
= Se to Te correlates with the increase of the interaction energy between the ChB donor and the

platinum complex from the Se to Te adducts.

Figure S13. QTAIM distribution of bond, ring, and cage critical points (red, yellow, and green

spheres, respectively) and bond paths in the calculated clusters.

Figure S14. The most important QTAIM distribution of bond and cage critical points (red and

green spheres, respectively) and bond paths in (a) [13·(4-NC5F4)2Se], (b) [13·(4-NC5F4)2Te], (c)

[2·(4-NC5F4)2Te].

18
Table S3. Electron density (b) at CCPs (in a.u.), and the ginter descriptor for the X-ray

structures calculated at the PBE0-D3BJ/ZORA-def2-TZVP level of theory.

Supramolecular
Contact ρb δginter
cluster
0.0055 0.0089
[13∙(4-NC5F4)2Se] π(I)··· π(III)
0.0038 0.0066
π(I)··· π(II) 0.0034 0.0055
π(I)··· π(III) 0.0060 0.0097
[13∙(4-NC5F4)2Te]
0.0038 0.0063
π(I)··· π(II)
0.0046 0.0076
[2∙(4-NC5F4)2Te] π(I)··· π(IITB) 0.0048 0.0080

In addition, results of the IGMH analysis40-43 (Figures S15–17) confirm that the C–Ch···Pt

ChB is of medium strength. This is evidenced by the presence of central areas of IGMH with light-

blue color that is particularly well observed in the case of Te adduct for the I···II interaction.

Moreover, the IGMH analysis shows that the C–Ch···Pt interaction energy should be comparable

to the Pt···Pt metallophilic interaction energy (Figure S15). By contrast, the green and thin IGMH

isosurfaces between the Сh and C atoms of the C–Ch···C contacts are regions with depleted

electron density indicating quite weak contacts and higher dispersion contribution in this

interaction. The IGMH analysis reveals the π–π interactions between the perfluorpyridyl and

diketonate fragments in 1·½(4-NC5F4)2Ch. Severe steric repulsions between the tBu groups and

the NC5F4 ring lead to a flip of the Pt complex relatively to the Te(C5F4N)2 moiety of 2·(4-

NC5F4)2Te. As a result, the -stacking is switched to the 2-phenylpyridine moiety, as indicated by

the QTAIM, HSA and IGMH analyses. The π–π interaction in 2·(4-NC5F4)2Te is weaker than that

in 1·½(4-NC5F4)2Ch while the opposite trend was found for the C–Ch···Pt interaction.

19
Figure S15. sign(λ2)ρ(r) function mapped on the δginter isosurface for the Pt···(Ch–C1D) and -

stacking interactions (δginter = 0.006 a.u. and blue-cyan-green-yellow-red color scale −0.05 <

sign(λ2)ρ(r) < 0.05).

Quite low values of ρb (0.011– 0.021 a.u.) and positive 2ρb (0.028– 0.050 a.u.), virtually

zero value of Hb and negative sign of λ2 (–0.0049, –0.0124 a.u.) (Table S4) at the BCP and results

of the IGMH analysis indicate that interactions between Ch and atoms Pt and C belong to medium

strength closed shell noncovalent interactions.44-47

20
Figure S16. The sign(2)(r) function mapped on the ginter isosurface for interactions C–Te···Pt

in 1·½(4-NC5F4)2Te; all isosurfaces are colored according to a BGR scheme over the ED range –

0.05 < sign(λ2)ρ > 0.05 a.u.

Figure S17. The sign(2)(r) function mapped on the ginter isosurface for interactions C–Te···Pt

in 2·(4-NC5F4)2Te; all isosurfaces are colored according to a BGR scheme over the ED range –

0.05 < sign(λ2)ρ > 0.05 a.u.

21
 Table S4. Electron density (b), its Laplacian (2b), potential and kinetic energy densities (Vb

and Gb), the curvature of ρ(r) (λ2) at BCPs (in a.u.), and the ginter descriptor for the X-ray structures

calculated at the PBE0-D3BJ/ZORA-def2-TZVP level of theory.

Supramolecular
Contact ρb 2ρb Vb Gb λ2 ginter
cluster/model
Se···Pt 0.0157 0.0347 –0.0082 0.0084 –0.0075 0.0251
[13∙(4-NC5F4)2Se]
Se···C30 0.0108 0.0277 –0.0055 0.0062 –0.0049 0.0189
Pt···Pt 0.0200 0.0489 –0.0121 0.0122 –0.0122 0.0367
Te···Pt 0.0236 0.0410 –0.0129 0.0116 –0.0128 0.0353
[13∙(4-NC5F4)2Te]
Te···C30 0.0144 0.0310 –0.0072 0.0075 –0.0067 0.0239
Pt···Pt 0.0206 0.0502 –0.0126 0.0126 –0.0124 0.0379
[2∙(4-NC5F4)2Te] Te···Pt 0.0329 0.0550 –0.0213 0.0175 –0.0208 0.0514

1·(4-NC5F4)2Se 0.0149 0.0343 –0.0079 0.0083 –0.0072 0.0240

IM1···II
Se···Pt
1·(4-NC5F4)2Te 0.0223 0.0423 –0.0125 0.0115 –0.0119 0.0332
Te···Pt
IM1···II
2·(4-NC5F4)2Te 0.0324 0.0560 –0.0211 0.0176 –0.0204 0.0506
Te···Pt
IM1···IITB

4.2 NBO and CDF analyses

For the better understanding the nature of the ChB, the second-order perturbation NBO

analysis using the NBO 7 program28 was performed. The second-order perturbation energy (E(2))

and change of the occupancy value of the *(Ch–C) orbitals (Δocc) were used to characterize the

contribution of charge transfer in non-covalent interactions.

The NBO analysis confirms that the found C–Ch···Pt and C–Ch···C interactions

correspond to the chalcogen bonding between the dz2 orbital of Pt and -orbital of C to the σ*(Ch–

C) antibonding orbitals. The calculated total energy E(2) for the orbital interaction LP dz2(Pt) →

σ*(Ch–C) is higher than for the π (Acac) → σ*(Ch–C) one (Table S5). It is worth noting that

reverse charge transfer from lone pairs of chalcogen to the metal or ligand orbital also gives a

contribution to the ChB stabilization. However, the direct charge transfer is a dominant factor in

the formation of chalcogen bonds of this type. The charge transfers and the E(2) energies increase

in overall with the increasing of the chalcogen donor atomic number, correlating with the stronger

Ch∙∙∙Pt/C chalcogen bond for Ch = Te. This is consistent with results obtained from the analysis
22
of the interaction energies discussed below. This effect is also consistent with the more positive

value of MEP (Figure S18) on the σ-hole of Te atom compared to the Se one48 and indicates

importance of electrostatic interaction to the formation of the Ch∙∙∙Pt/C interaction.49

Figure S18. Molecular electrostatic potential (MEP) surface (0.001 a.u.) of (4-NC5F4)2Ch (a) Se

and (b) Te at the PBE0-D3BJ/def2-TZVP level of theory. The calculated maximum positive

electrostatic potentials (Vs,max) of the studied molecules are given in kcal/mol. The color scheme

is taken from Politzer and Murray.50

Table S5. Second order NBO perturbation energies (E(2), in kcal/mol), change of the occupancy

of the *(Ch–C) NBO upon the formation of ChB (occ *(Ch–C), in me) and charge transfer

(Δq(CDF), in me) from the CDF analysis calculated for the X-ray geometries at the PBE0-

D3BJ/ZORA-def2-TZVP level of theory.

Supramolecular occ
Contact Transition E(2) Δq(CDF)
cluster/model *(Ch–C)
(Acac)  σ*(Se–C) 2.5 24
[13∙(4-NC5F4)2Se]
Se···C(Acac) LP(Se)  *(Acac) 0.6 35

LP(Pt2)  σ*(Se–C1D/C6D) 3.4/0.2

[13∙(4-NC5F4)2Se]
Se···Pt LP(Se)  LV(Pt2) 0.5 48 75
LP(Pt2)  π*(C1D–C2D) 0.9

23
 [13∙(4-NC5F4)2Se] LP(Pt3)  LP(Pt2) 2.5
Pt···Pt 35
LP(Pt2)  LP(Pt) 2.0
[13∙(4-NC5F4)2Te] (Acac)  σ*(Te–C)
4.5
Te···C(Acac) LP(Te)  *(Acac) 50 45
0.7
LP(Pt2)  σ*(Te–C1D/C6D) 6.0/1.0
[13∙(4-NC5F4)2Te] LP(Te)  LV(Pt2) 1.6
Te···Pt 93 107
LP(Pt2)  π*(C1D–C2D) 0.7

[13∙(4-NC5F4)2Te] LP(Pt3)  LP(Pt2) 2.6

Pt···Pt 45
LP(Pt2)  LP(Pt) 1.8
[2∙(4-NC5F4)2Te] LP(Pt1)  σ *(Te–C) 11.0
Te···Pt 105 110
LP(Te)  LV(Pt1) 3.2
Model
LP(Pt)  σ*(Se-C) 3.7
1·(4-NC5F4)2Se
Se···Pt σ*(Pt–C/N)  σ*(Se–C) 1.2/0.5 33
IM1···II
LP(Se)  LV(C) 1.4

LP(Pt)  σ*(Te-C) 6.4

1·(4-NC5F4)2Te
Te···Pt σ*(Pt–C/N)  σ*(Te–C) 2.3/1.0 70
IM1···II
LP(Te)  LV(C) 2.9

LP(Pt2)  σ*(Te–H/C) 0.5/10.4

2·(4-NC5F4)2Te
Te···Pt σ*(Pt–C/N)  σ*(Te–C) 2.5/1.0 98
IM1···IITB
LP(Te)  σ*(Pt–C/N) 0.7/1.5

In order to provide further insight into the electron density changes and charge transfers

upon formation of the chalcogen bonds, the electron density difference (EDD) maps were

constructed and the charge displacement function (CDF) analysis51 was performed. Figure S20–

22 shows a graph of the EDD plot obtained as a result of subtraction of the electron density

between the cluster and the initial monomers and the sum of isolated fragments, all being in the

same positions as in the complex. The EDD plots (Figure S19) also show that polarization effects

caused by the positive σ-hole at the Ch atom tend to shift the electron density from the donor atoms

(Pt/C) and, hence, to increase the electron density in the intermolecular space between the Ch and

Pt atoms.

24
Figure S19. Electron density difference (EDD) maps for [13∙(4-NC5F4)2Se] and [13∙(4-NC5F4)2Te].

Electrons transfer from the electron density decreased regions (blue) to increased regions (red).

The isovalues 0.0008 EDD maps.

By integrating Δρ along the axis z passing through the three atoms Ch–Pt–Pt, (according

to equation:

+∞ +∞ 𝑧′
∆𝑞(𝑧′) = ∫ ―∞
∫
𝑑𝑥
―∞
∫
𝑑𝑦
―∞
𝑑𝑧∆𝜌(𝑥,𝑦,𝑧)

, the CDF can be computed in each point, therefore allowing us to quantitatively analyze the charge

transfers (Δq) and the polarization within each fragment. The charge transfer values were taken as

Δq value at the isodensity boundary, which is the point along the z’ axis at which the electron

densities of the non-interacting fragments meet with equal value. Δρ(x,y,z) is the difference

between the electron density of a complex and of the isolated fragments with unrelaxed geometries

corresponding to those in the complex. The CDF curves for 1·½(4-NC5F4)2Ch is negative, thus

describing a net displacement of electrons from Pt to Pt and corresponds to CT of 35 me (for Se)

and 45 me (for Te). The CT from the C atom of the acac moiety is 30 me (for Se) and 45 me (for

Te) being much lower than for metal-involving ChB (Figure S21). It should be noted that in ChB,

25
the charge transfer occurs from the platinum to the chalcogen and neighbor carbon atom. For the

Pt–Ch interactions, CT values are 75 me (Se) and 107 me (Te) for 1·½(4-NC5F4)2Ch, and 110 me

for 2·(4-NC5F4)2Te and they are in a good agreement with the population of the σ*(Se–C) NBOs

(48 me (Se) and 93 me (Te) for 1·½(4-NC5F4)2Ch, 105 me for 2·(4-NC5F4)2Te)). In all cases, the

CT values increase with the growth of the chalcogen atomic number.

Figure S20. (a) CDF functions for the C–Te···Pt···Pt and C–Te···Pt interaction 1∙(4-NC5F4)2Te

adduct. Black dots indicate the z position of the atomic nuclei; Contour plots of the EDD. The

positive (red) and negative (blue) contour levels range from ±0.0002 to 0.01 with a step of 0.0005;

The light gray vertical line identifies the boundary between the two fragments. (b) EDD maps

corresponding to  = (Pt3TePt2Pt1)  (Pt3Te) – (Pt2) – (Pt1). Electrons transfer

from the electron density decreased regions (blue) to increased regions (red). The isovalues 0.0008

EDD maps. (in a.u.)

26
Figure S21. CDF functions for the C–Te···C(Acac) interaction 2∙(4-NC5F4)2Te adduct. Black dots

indicate the y position of the atomic nuclei; Contour plots of the EDD. The positive (red) and

negative (blue) contour levels range from ±0.0002 to 0.01 with a step of 0.0005; the light gray

vertical line identifies the boundary between the two fragments.

Figure S22. CDF functions for the C–Te···Pt interaction 1∙(4-NC5F4)2Te adduct. Black dots

indicate the y position of the atomic nuclei; Contour plots of the EDD. The positive (red) and

negative (blue) contour levels range from ±0.0002 to 0.01 with a step of 0.0005; The light gray

vertical line identifies the boundary between the two fragments.

27
4.3 Interaction energies and SAPT-based decomposition
The SAPT0 method is used to assess the energy of non-covalent interactions and their

components.40,41

Table S6 SAPT. Results of the SAPT0 analysis (energies in kcal/mol)

Interacting
Contact Eelec Eind Eexch Edis ECT Eint(SAPT)
fragments
(Se···Pt) I···II –14.7 –5.4 24.9 –23.4 0.9 –18.6
(Te···Pt) I···II –21.4 –8.2 30.2 –26.5 2.3 –25.9
(Te···Pt) I···IITB –28.6 –10.0 39.9 –31.9 5.4 –30.6
(Se···C) I···III –13.1 –6.2 19.1 -18.8 0.6 –19.0
(Te···C) I···III –16.1 –6.7 22.9 –21.5 0.8 –21.5
(Pt···Pt) in 1∙(4-NC5F4)2Se –16.7 –4.0 31.9 –36.3 1.1 –25.1
(Pt···Pt) in 1∙(4-NC5F4)2Te –17.8 –3.9 33.7 –37.8 1.2 –25.7

SAPT is one of rigorous methods for indirect estimate of interaction energies in systems

with multiple noncovalent interactions allowing also decomposition of (Eint) into its components

(i.e. electrostatic (Eels), exchange (Eexch), induction (Eind), and dispersion (Edis) terms). Here, the

SAPT0 level of theory was used to determine Eint between bimolecular fragments at the X-ray

structures (Figure S23). The total SAPT interaction energies for the investigated dimers are

presented in Table S6. The interaction energy for the bimolecular fragments increases with an

increasing of chalcogen atomic number. To estimate the contribution of the paired Ch···Pt

interaction in Eint we used the supermolecular approach. The energy values for the Ch···Pt

interaction are higher than those for the Ch···C one and fall within the range of –30.6 to –18.6

kcal/mol and they provide ca. 60% (Ch = Se) and 50% (Ch = Te) of Eint. The results of

decomposition of the interaction energies in bimolecular fragments reveal that the main

contributors to interactions are dispersion and electrostatic components. The dispersion effect

dominates in the attractive part of the interaction energy, and in the most of these cases, it even

contributes more than 50% to this part due to big interaction area between the perfluoropyridine

moieties and the platinum complex. This trend persists for model fragmented molecules at

supermolecular approach procedure. (Table S7) The electrostatic component is also quite

significant (24–38%). The induction term as defined in the SAPT theory reflects both charge

28
polarization and charge transfer effects, and its contribution to the bonding is negligible. Also, the

charge transfer was separately assessed using the SAPT method as described by Stone and Miskitta

are presented in Table S6.52 It should be noted that the contribution of induction increases from

the Se to the Te adducts that is conceivably due to an increase of CT as a result of the donor-

acceptor interaction Pt/C → σ-holes-Ch–С. This is consistent with the results of the NBO analysis.

Figure S23. Decomposition interaction energies bimolecular fragments for adducts 1·½(4-

NC5F4)2Se and 1·½(4-NC5F4)2Te. Bar color correspond to the percentage of each stabilizing

contribution (Eelst + Eind + Edis = 100%).

29
Table S7. Results of the SAPT0 analysis (energies in kcal/mol). Eelec is electrostatic, Eexch –

exchange, Eind – induction, Edis – dispersion terms.

IM1···II/IITB IM2···II/IITB I···II/IITB IM1···III IM2···III I···II

1·(4-NC5F4)2Se
Eelec –7.8 –8.9 –14.7 –6.4 –8.3 –13.1
Eexch 12.7 14.6 24.9 8.2 14.7 19.1
Eind –3.0 –2.2 –5.4 –1.9 –1.9 –6.2
Edis –10.3 –14.5 –23.4 –5.1 –16.0 –18.8
Eint(SAPT) –8.4 –11.0 –18.6 –5.2 –11.5 –19.0
1·(4-NC5F4)2Te
Eelec –12.3 –8.6 –21.4 –8.4 –8.3 –16.1
Eexch 21.6 14.1 30.2 12.2 14.3 31.9
Eind –6.8 –2.2 –5.4 –3.9 –1.8 –4.0
Edis –16.2 –13.9 –26.5 –7.9 –16.1 –36.3
Eint(SAPT) –13.6 –10.6 –25.9 –8.0 –11.9 –21.5
2·(4-NC5F4)2Te
Eelec –16.7 –9.0 –28.6
Eexch 29.9 15.1 39.9
Eind –10.1 –2.1 –10.0
Edis –20.1 –15.9 –31.9
Eint(SAPT) –16.9 –11.9 –30.6

4.4 Supermolecular approach

The overall interaction energies between fragments I and II at the XRD geometries,

Eint(I···II)X-ray, were calculated for the bimolecular clusters I···II as the BSSE corrected energy

difference Eint(I···II)X-ray = E(I···II)X-ray – E(I)X-ray – E(II)X-ray, where E(I···II)X-ray, E(I)X-ray, and

E(II)X-ray are energies of I···II and isolated fragments I and II at the X-ray geometries.

The overall interaction energies between fragments I and II at the optimized geometries,

Eint(I···II)opt, were calculated for the bimolecular clusters I···II as the BSSE corrected energy

difference Eint(I···II)opt = E(I···II)opt – E(I)opt,unrelx – E(II)opt,unrelx, where E(I···II)opt, E(I)opt,unrelx, and

E(II)opt,unrelx are energies of the fully optimized cluster I···II and those of the fragments I and II

with unrelaxed geometries corresponding to the optimized cluster I···II.

The overall binding energies between fragments I and II at the optimized geometries,

Eb(I···II)opt, were calculated for the bimolecular clusters I···II as the BSSE corrected energy

30
difference Eint(I···II)opt = E(I···II)opt – E(I)opt,relx – E(II)opt,relx, where E(I···II)opt, E(I)opt,relx, and

E(II)opt,relx are energies of the fully optimized cluster I···II and fragments I and II.

The same procedures were applied for the calculations of the overall interaction and

binding energies in the clusters I···IITB and I···III.

To separate energies of the paired Ch···Pt interactions, Eint(Ch···Pt)X-ray, the model clusters

IM1···II/IITB and IM2···II/IITB were calculated (Figure S24). In these models, where either the

Ch···C1D and -stacking or the Ch···Pt interactions were switched off. In IM1, the NC5F4 moiety

of the (NC5F4)2Ch molecule was replaced by the hydrogen atom with the C–H distance of 1.09 Å.

In IM2, the ChNC5F4 moiety of the (NC5F4)2Ch molecule was replaced by the hydrogen atom with

the Se/Te–H distance of 1.46/1.69 Å.

31
Figure S24. X-ray and optimized structures 1·½(4-NC5F4)2Se and 2·(4-NC5F4)2Te.

32
Figure S25. QTAIM distribution of bond, ring, and cage critical points (red, yellow, and green

spheres, respectively) and bond paths in the calculated models for 1·(4-NC5F4)2Se, 1·(4-

NC5F4)2Te and 2·(4-NC5F4)2Te (top); sign(λ2)ρ(r) function mapped on the δginter isosurface for the

models (δginter = 0.006 a.u. and blue-cyan-green-yellow-red color scale −0.05 < sign(λ2)ρ(r) <

0.05)( down).

4.5 Cartesian coordinates for the studied molecules

4.5.1 Optimized geometries
All geometries given below were optimized under PBE0-D3BJ/DZP level using Gaussian 16 with

ultrafine integration grid was applied for numerical integrations. Energy is given for the basis

DZP-DKH.

Cartesian coordinate for 1 (in Å)

E = –19195.26552

33
 Pt -0.343848000 -0.021337000 -0.168078000
O -1.729169000 -1.463255000 -0.090359000
O -1.802312000 1.446534000 -0.081972000
N 1.147764000 1.282339000 -0.041730000
C 1.139291000 -1.285146000 0.011652000
C 0.980939000 2.616931000 -0.030413000
H -0.055347000 2.955729000 -0.111936000
C 2.410060000 0.761108000 0.070352000
C 2.432149000 -0.692773000 0.065520000
C 2.039620000 3.503558000 0.079019000
H 1.844487000 4.577943000 0.081196000
C 1.096347000 -2.688921000 0.008924000
H 0.122854000 -3.186815000 -0.030885000
C -3.040215000 1.222556000 0.122622000
C 2.255788000 -3.455651000 0.092398000
H 2.183055000 -4.548559000 0.096076000
C -2.976287000 -1.285049000 0.120450000
C -3.635814000 -0.047887000 0.218076000
H -4.710574000 -0.077569000 0.403906000
C 3.514910000 -2.846374000 0.159118000
H 4.422031000 -3.454124000 0.221116000
C 3.512759000 1.614210000 0.181568000
H 4.510837000 1.180975000 0.270363000
C 3.334354000 2.989917000 0.185396000
H 4.195435000 3.658580000 0.272533000
C -3.894702000 2.450146000 0.258439000
H -3.809693000 3.054398000 -0.660483000
H -4.952066000 2.211037000 0.438538000
H -3.515040000 3.068243000 1.089502000
C 3.601300000 -1.460250000 0.150012000
H 4.582680000 -0.977737000 0.201229000
C -3.763242000 -2.556268000 0.250980000
H -3.370159000 -3.141332000 1.099494000
H -4.836158000 -2.373565000 0.401623000
H -3.618261000 -3.166182000 -0.656136000

Cartesian coordinate for 2 (in Å)

34
E = – 18373.3171539

Pt 0.410205000 -0.006353000 -0.260114000

O -0.966729000 -1.449011000 -0.223556000
O -1.055519000 1.444894000 -0.216518000
C 1.889086000 -1.265099000 -0.013764000
N 1.887891000 1.303948000 -0.049096000
C 1.854315000 -2.668891000 -0.038473000
H 0.887817000 -3.170946000 -0.141357000
C 3.143515000 0.787219000 0.133683000
C 3.173497000 -0.666796000 0.117822000
C -2.293728000 1.222052000 -0.007764000
C 3.011126000 -3.431318000 0.100466000
H 2.944441000 -4.524518000 0.085232000
C -2.214010000 -1.286447000 0.001511000
C -2.963292000 -2.609651000 0.162687000
C -3.134487000 2.493679000 0.128605000
C 4.340088000 -1.429910000 0.258839000
H 5.314588000 -0.943666000 0.370431000
C 1.714163000 2.637390000 -0.037536000
H 0.683162000 2.971152000 -0.180488000
C 2.759342000 3.528177000 0.142748000
H 2.558982000 4.601596000 0.141461000
C 4.047818000 3.019298000 0.323532000
H 4.898605000 3.691060000 0.468493000
C 4.260858000 -2.816547000 0.246552000
H 5.166414000 -3.420525000 0.352283000
C 4.233141000 1.644491000 0.318713000
H 5.226292000 1.215313000 0.464341000
C -2.877315000 -0.052253000 0.097964000
H -3.944848000 -0.088100000 0.288787000
C -2.697715000 -3.452517000 -1.091970000
H -3.107803000 -2.963621000 -1.992350000
H -3.179379000 -4.439866000 -0.990833000
H -1.617968000 -3.600040000 -1.243876000
C -4.619407000 2.225364000 0.361544000
H -5.072128000 1.661890000 -0.470955000
35
 H -5.156593000 3.185119000 0.442516000
H -4.796783000 1.668021000 1.296161000
C -2.373125000 -3.315658000 1.392442000
H -1.288207000 -3.463607000 1.278235000
H -2.850906000 -4.300920000 1.528291000
H -2.543166000 -2.723961000 2.308311000
C -2.572046000 3.289704000 1.314625000
H -2.673949000 2.723196000 2.256096000
H -3.119550000 4.241003000 1.427203000
H -1.504709000 3.515971000 1.167703000
C -4.469094000 -2.440882000 0.348870000
H -4.712663000 -1.874584000 1.263034000
H -4.938612000 -3.434259000 0.442656000
H -4.936626000 -1.932980000 -0.510996000
C -2.962774000 3.302262000 -1.164509000
H -1.900121000 3.516042000 -1.356107000
H -3.506697000 4.259168000 -1.087859000
H -3.362534000 2.750913000 -2.032759000

Cartesian coordinate for (4-NC5F4)2Se (in Å)

E = – 3718.55186117

Se -0.000037000 -1.758621000 -0.000007000

F -0.261705000 0.787262000 -1.833066000
F 0.261821000 0.787023000 1.833263000
F -2.748294000 -1.669175000 1.364783000
F 4.766556000 0.085769000 -0.973085000
F -2.384377000 2.442543000 -2.043332000
F 2.748135000 -1.669017000 -1.365108000
F -4.766634000 0.085707000 0.972887000
F 2.384543000 2.442229000 2.043619000
N -3.560144000 1.252798000 -0.531524000
N 3.560183000 1.252641000 0.531587000
C -1.348632000 0.568707000 -1.100056000
C -1.412381000 -0.503986000 -0.207721000
C -2.601975000 -0.669501000 0.502948000
C 1.348702000 0.568525000 1.100171000
C 2.448373000 1.417493000 1.207969000
C -2.448267000 1.417718000 -1.207814000
C 3.639567000 0.239273000 -0.296379000
C 2.601921000 -0.669489000 -0.503085000
36
 C -3.639593000 0.239311000 0.296292000
C 1.412384000 -0.504058000 0.207700000

Cartesian coordinate for (4-NC5F4)2Te (in Å)

E = –8075.43856779

Te -0.000005000 -1.711183000 -0.000004000

F -2.948558000 -1.599768000 1.208681000
F -0.316414000 1.092326000 -1.666973000
F -2.419553000 2.764641000 -1.839875000
F 0.316362000 1.092043000 1.666962000
F 2.948679000 -1.599619000 -1.208926000
F -4.936904000 0.193347000 0.876829000
F 4.936935000 0.193545000 -0.876845000
F 2.419449000 2.764455000 1.840096000
N 3.666126000 1.469218000 0.479519000
N -3.666167000 1.469241000 -0.479399000
C -1.536647000 -0.325732000 -0.206119000
C 1.536723000 -0.325810000 0.206024000
C -1.435380000 0.813486000 -1.003040000
C 3.782021000 0.394041000 -0.261847000
C 1.435372000 0.813319000 1.003075000
C -3.782004000 0.393960000 0.261846000
C -2.525363000 1.677300000 -1.092125000
C -2.755703000 -0.533585000 0.436900000
C 2.525315000 1.677166000 1.092278000
C 2.755766000 -0.533550000 -0.437024000

Cartesian coordinate of model I···II for 1·(4-NC5F4)2Se (in Å)

E = –22914.0908415

37
Se 1.036029000 -0.723941000 0.313003000
F 2.101841000 1.384154000 -1.708997000
F -0.221143000 1.201947000 2.413003000
F 3.124901000 0.710245000 2.242003000
F 3.022172000 -2.339765000 -1.384997000
F 5.809924000 0.454483000 2.231003000
F 5.713185000 -2.479525000 -1.192997000
F 1.942602000 4.074140000 -1.550997000
F -0.245382000 3.896945000 2.390003000
N 5.744054000 -1.009523000 0.517003000
N 0.855612000 3.965043000 0.425003000
C 0.936860000 1.174050000 0.348003000
C 5.047115000 -1.691585000 -0.358997000
C 0.323800000 1.851996000 1.401003000
C 5.094984000 -0.225580000 1.346003000
C 1.500791000 1.950100000 -0.664997000
C 2.954035000 -0.791771000 0.410003000
C 3.658109000 -1.622708000 -0.460997000
C 3.707972000 -0.085704000 1.348003000
C 0.321676000 3.245995000 1.382003000
C 1.425668000 3.337094000 -0.573997000
Pt -2.042022000 -0.156215000 -0.475997000
O -2.589181000 1.630737000 0.242003000
O -1.303099000 0.710851000 -2.204997000
C -1.544857000 -2.006170000 -1.029997000
N -2.534938000 -1.103259000 1.168003000
C -0.967831000 -2.302119000 -2.206997000
H -0.784907000 -1.448103000 -2.863997000
C -1.785769000 -2.998192000 -0.119997000
C -2.372812000 -2.514244000 1.120003000
C -0.613716000 -3.594088000 -2.556997000
H -0.143700000 -3.781046000 -3.524997000
C -3.084985000 -0.570307000 2.343003000
H -3.221081000 0.511681000 2.420003000
C -1.267210000 1.964854000 -2.430997000
C -3.427912000 -1.386338000 3.419003000
38
 H -3.846952000 -0.938375000 4.326003000
C -2.417281000 2.756752000 -0.341997000
C -1.791299000 2.958808000 -1.583997000
H -1.694391000 3.992816000 -1.917997000
C -3.249789000 -2.773322000 3.351003000
H -3.523733000 -3.408346000 4.199003000
C -1.448652000 -4.321162000 -0.426997000
H -1.644582000 -5.103179000 0.308003000
C -0.862625000 -4.625110000 -1.646997000
H -0.593533000 -5.657086000 -1.887997000
C -0.591246000 2.365914000 -3.708997000
H -1.080201000 1.855871000 -4.554997000
H -0.611343000 3.451913000 -3.872997000
H 0.457784000 2.024008000 -3.683997000
C -2.718739000 -3.338275000 2.199003000
H -2.575643000 -4.422262000 2.142003000
C -2.967385000 3.932703000 0.407003000
H -2.695379000 3.857727000 1.472003000
H -2.611470000 4.888735000 0.001003000
H -4.069383000 3.905605000 0.348003000

Cartesian coordinate of model I···II for 1·(4-NC5F4)2Te (in Å)

E = –27270.9866055

Pt -2.107487000 0.032372000 -0.413094000

Te 0.850420000 -0.897513000 0.173294000
F -0.033571000 1.330228000 2.377620000
F 2.047606000 1.283177000 -1.877649000
F 2.221463000 3.959605000 -1.696907000
O -2.379418000 1.865914000 0.339060000
F 3.076393000 0.346245000 2.267076000
F 3.110437000 -2.447194000 -1.562962000
O -1.420490000 0.819667000 -2.200329000
F 0.278694000 3.999596000 2.374324000
F 5.787838000 -2.593218000 -1.289307000
39
 F 5.757479000 0.086130000 2.338846000
N -1.954702000 -1.863363000 -1.017912000
C -2.588641000 -0.857696000 1.267623000
N 5.755129000 -1.249883000 0.521961000
N 1.251906000 3.961878000 0.340852000
C -1.534854000 -2.221481000 -2.242990000
H -1.288624000 -1.393063000 -2.912252000
C 0.977193000 1.178164000 0.239859000
C -2.249343000 -2.821653000 -0.088867000
C 2.965960000 -1.024658000 0.331679000
C -2.957057000 -0.266282000 2.483033000
H -2.914897000 0.822270000 2.576300000
C 1.574620000 1.894334000 -0.793227000
C 5.089718000 -1.866728000 -0.425114000
C 3.688436000 -0.391026000 1.340284000
C -1.408988000 -3.545495000 -2.626563000
H -1.063741000 -3.784830000 -3.634181000
C -3.334626000 -1.038129000 3.579358000
H -3.604602000 -0.546457000 4.519664000
C -1.713873000 -4.541644000 -1.695651000
H -1.618348000 -5.598585000 -1.959853000
C -3.037202000 -3.054666000 2.295926000
H -3.072031000 -4.145911000 2.221432000
C 0.696609000 3.297785000 1.326903000
C 1.678546000 3.280037000 -0.693197000
C -2.136853000 2.969102000 -0.264273000
C 0.528123000 1.914480000 1.332285000
C 5.074582000 -0.528810000 1.381607000
C 3.704908000 -1.789102000 -0.567273000
C -2.654881000 -2.275225000 1.196900000
C -3.380090000 -2.434207000 3.490302000
H -3.680018000 -3.033871000 4.354119000
C -1.251280000 2.061942000 -2.431766000
C -2.132717000 -4.174094000 -0.425034000
H -2.366549000 -4.930643000 0.326231000
C -2.510678000 4.194012000 0.514267000
H -3.608972000 4.304778000 0.491389000
H -2.053680000 5.104113000 0.102040000
H -2.215614000 4.073800000 1.567617000
C -0.625579000 2.387155000 -3.755132000
H 0.395791000 1.970741000 -3.778129000
H -0.576064000 3.468509000 -3.942366000
H -1.196364000 1.896737000 -4.560474000
C -1.587785000 3.105344000 -1.549136000
H -1.403698000 4.123061000 -1.895852000

Cartesian coordinate of model I···IIТБ for 2·(4-NC5F4)2Te (in Å)

E = – -27506.7096027

40
Pt -1.883823 0.862773 0.349490
O -0.910447 2.178922 1.498906
O -1.657473 2.089923 -1.294328
C -1.880746 -0.544892 1.717859
N -2.890353 -0.538356 -0.650464
C -1.281932 -0.519013 2.983771
H -0.706403 0.363007 3.277632
C -3.169443 -1.690930 0.030801
C -2.607355 -1.716286 1.372704
C -0.766118 2.998094 -1.370117
C -1.361534 -1.611434 3.844789
H -0.863117 -1.570352 4.818448
C -0.227800 3.175751 1.077442
C 0.527531 3.905266 2.187168
C -0.438940 3.426212 -2.798949
C -2.691531 -2.814768 2.236164
H -3.231528 -3.718703 1.938880
C -3.331242 -0.381922 -1.909632
H -3.047287 0.558100 -2.389054
C -4.071812 -1.351986 -2.563155
H -4.399274 -1.180154 -3.590215
C -4.370396 -2.535013 -1.883656
H -4.946878 -3.326641 -2.369573
C -2.065082 -2.763319 3.475894
H -2.115569 -3.620958 4.151548
C -3.917260 -2.699616 -0.582968
H -4.126629 -3.617898 -0.031833
C -0.099906 3.563190 -0.265890
H 0.585009 4.379134 -0.472148
C -0.424964 4.098238 3.372982
H -1.278561 4.740482 3.096555
H 0.110976 4.582767 4.205921
H -0.823292 3.134635 3.722177
C 0.562979 4.575156 -2.878043
H 0.192227 5.482975 -2.373557
H 0.740415 4.832844 -3.935202
H 1.536874 4.304022 -2.438418
C 1.695544 2.997526 2.604331

41
 H 1.340506 2.002919 2.914812
H 2.240753 3.454230 3.447871
H 2.410437 2.857938 1.776313
C 0.153141 2.185699 -3.488959
H 1.060519 1.835851 -2.969964
H 0.417409 2.426046 -4.532616
H -0.566062 1.352366 -3.489909
C 1.072671 5.263645 1.749949
H 1.847482 5.172218 0.971255
H 1.540618 5.763228 2.614177
H 0.274515 5.923578 1.371351
C -1.742175 3.836983 -3.493860
H -2.485676 3.026895 -3.448692
H -1.545665 4.072738 -4.553253
H -2.180850 4.732281 -3.020841
Te 1.153261 0.199840 0.000040
F 2.602490 -1.480579 -2.407581
F 5.164380 -2.262048 -2.727078
F 3.928432 0.491970 1.693690
F 6.427699 -0.363628 1.164128
F 1.368866 -2.312192 1.993719
F -0.425038 -1.464033 -2.308324
F -1.351948 -3.994016 -2.293764
N 5.777816 -1.308626 -0.777284
F 0.330440 -4.794518 1.812049
C 0.480133 -1.760022 -0.133432
C 5.457760 -0.630127 0.298503
C 3.503247 -1.177567 -1.472687
C 0.684254 -2.657108 0.910729
C 4.826921 -1.578802 -1.640400
C 3.141146 -0.466776 -0.330770
C -0.208455 -2.232797 -1.246005
C 4.163122 -0.189604 0.572638
C -0.683971 -3.541690 -1.238004
N -0.514200 -4.367660 -0.233713
C 0.157268 -3.943493 0.810484

Cartesian coordinate of model I···III for 1·(4-NC5F4)2Se (in Å)

E = –22914.0897932

42
Pt 2.058640000 -0.503818000 0.787197000
Se -2.523228000 -1.395993000 0.058323000
F -3.504934000 0.075906000 -2.550899000
F -4.509611000 -0.184982000 2.072433000
F -1.552926000 1.526228000 0.577929000
F -0.572495000 -2.171294000 -2.210377000
O 1.862978000 -2.399948000 -0.031630000
F 0.304636000 2.916435000 -0.806486000
F 1.333900000 -0.647927000 -3.365683000
F -5.528017000 1.850626000 -2.773441000
F -6.508320000 1.576759000 1.619413000
O 0.628828000 -0.894272000 2.136782000
C 3.414320000 0.086156000 -0.545673000
N 0.801243000 1.127441000 -2.080707000
N -6.002604000 1.701125000 -0.574243000
N 2.197044000 1.379099000 1.315101000
C 3.936394000 -0.715674000 -1.489226000
H 3.564559000 -1.743529000 -1.485956000
C -3.912702000 -0.121170000 -0.221480000
C 1.503542000 2.046040000 2.335691000
H 0.764594000 1.492511000 2.922663000
C 0.593456000 -0.127991000 -2.394374000
C -4.718126000 0.280727000 0.844491000
C 0.094568000 1.647990000 -1.106236000
C -4.206586000 0.418307000 -1.475472000
C -1.158251000 -0.373588000 -0.780080000
C -0.381085000 -0.921891000 -1.798209000
C 3.143686000 2.142250000 0.578595000
C 4.737450000 1.893738000 -1.394800000
H 5.032236000 2.942917000 -1.334512000
C 4.865648000 -0.273111000 -2.415503000
H 5.252196000 -0.966933000 -3.164527000
C -0.049315000 -1.970852000 2.222350000
C -0.882191000 0.940329000 -0.405445000
C 2.645033000 4.131744000 1.847068000
H 2.806063000 5.193416000 2.053770000
43
 C 3.802771000 1.396956000 -0.482079000
C 3.358304000 3.501806000 0.835002000
H 4.082070000 4.073376000 0.245584000
C 5.274819000 1.060991000 -2.365444000
H 6.004176000 1.448107000 -3.082484000
C -5.746779000 1.191434000 0.606364000
C 0.993422000 -3.259274000 0.327202000
C 1.714755000 3.398776000 2.592848000
H 1.149453000 3.893170000 3.389886000
C -5.254048000 1.330746000 -1.586120000
C 0.070266000 -3.092767000 1.378489000
H -0.600221000 -3.929676000 1.580530000
C 0.992141000 -4.536068000 -0.460869000
H 0.851581000 -4.300737000 -1.528427000
H 0.206877000 -5.231946000 -0.134681000
H 1.976116000 -5.023869000 -0.358418000
C -1.046042000 -1.985920000 3.342784000
H -1.642881000 -2.908178000 3.361622000
H -1.717781000 -1.117597000 3.244218000
H -0.507458000 -1.880315000 4.299660000

Cartesian coordinate of model I···III for 1·(4-NC5F4)2Te (in Å)

E = – 27270.9812070

Te -2.467615000 -1.275070000 -0.249500000

F -5.056782000 -0.866517000 1.642775000
F -3.141162000 1.378425000 -2.067257000
F -5.143727000 3.167951000 -1.871545000
F -1.354439000 0.578422000 2.144249000
F -0.478952000 0.028562000 -2.482201000
F -6.980908000 1.018569000 1.641227000
F 1.181503000 2.127512000 -2.297591000
F 0.331794000 2.674444000 2.093937000
N 0.741868000 2.389154000 -0.103580000
44
 N -6.047075000 2.083337000 -0.112984000
C -3.991135000 0.179851000 -0.201984000
C -1.010377000 0.214157000 -0.175887000
C -4.054874000 1.236666000 -1.109006000
C 0.545008000 1.715367000 -1.208026000
C -0.750721000 0.903937000 1.006001000
C -6.012696000 1.086522000 0.738169000
C -5.094497000 2.159783000 -1.011821000
C -5.015325000 0.111340000 0.740386000
C 0.127735000 1.988137000 0.983317000
C -0.313237000 0.622398000 -1.307318000
Pt 2.273833000 -0.913839000 0.182875000
O 1.115537000 -1.858528000 1.522694000
O 1.499106000 -2.053806000 -1.369049000
N 3.363467000 0.230168000 -1.029704000
C 4.237010000 0.842035000 -3.171911000
H 4.300031000 0.626555000 -4.240306000
C 3.486505000 0.017647000 -2.351180000
H 2.936213000 -0.843377000 -2.738877000
C 3.998850000 1.295654000 -0.451547000
C 2.904346000 0.394966000 1.498443000
C 2.642089000 0.433655000 2.874865000
H 1.976030000 -0.317573000 3.309494000
C 0.217859000 -2.719911000 1.254272000
C 4.762173000 2.162702000 -1.238731000
H 5.253247000 3.015109000 -0.766051000
C 3.776236000 1.391690000 0.982620000
C 4.314350000 2.395411000 1.796531000
H 4.967878000 3.165282000 1.374590000
C -0.551145000 -3.213289000 2.442430000
H -1.039105000 -2.355571000 2.934175000
H -1.314500000 -3.954776000 2.170699000
H 0.151519000 -3.654167000 3.168643000
C 3.179834000 1.428802000 3.688657000
H 2.944866000 1.439655000 4.758043000
C 4.018988000 2.412364000 3.154275000
H 4.435451000 3.192885000 3.796910000
C 0.528304000 -2.864531000 -1.250398000
C 4.886618000 1.939076000 -2.602049000
H 5.482293000 2.616929000 -3.219782000
C -0.101505000 -3.206079000 -0.032468000
H -0.892132000 -3.956559000 -0.085387000
C 0.020619000 -3.461228000 -2.529353000
H 0.863015000 -3.897219000 -3.090070000
H -0.747855000 -4.228168000 -2.360589000
H -0.406941000 -2.654867000 -3.149101000

Cartesian coordinate of model IM1···II for 1·(4-NC5F4)2Se (in Å)

E = –21183.3947434

45
Se 1.261612000 0.035272000 -0.009542000
F 2.893616000 -2.251240000 1.514644000
F 6.241767000 1.368852000 -0.578730000
F 3.580557000 1.727753000 -0.954482000
F 5.574873000 -2.422502000 1.774727000
N 5.897840000 -0.525917000 0.597898000
H 0.881579000 -1.134369000 0.770913000
C 3.676130000 -1.315435000 0.970339000
C 5.059207000 -1.400663000 1.102570000
C 5.391423000 0.485922000 -0.069034000
C 4.028204000 0.673663000 -0.264152000
C 3.120139000 -0.246221000 0.265591000
Pt -1.919793000 0.505973000 -0.138856000
O -1.074019000 2.070341000 -1.197706000
O -2.253840000 1.696285000 1.438846000
N -1.513551000 -0.827459000 -1.558537000
C -2.400435000 -1.126821000 0.834749000
C -1.747783000 -2.140381000 -1.252939000
C -2.277054000 -2.331590000 0.088543000
C -0.997703000 -0.506591000 -2.757787000
H -0.811138000 0.559003000 -2.914310000
C -0.739812000 3.185140000 -0.679392000
C -3.233460000 -2.483344000 2.683944000
H -3.617326000 -2.539957000 3.708033000
C -2.905307000 -1.244415000 2.138846000
H -3.015547000 -0.340640000 2.745469000
C -1.463588000 -3.138224000 -2.190474000
H -1.652548000 -4.181189000 -1.929535000
C -0.702990000 -1.455724000 -3.721744000
H -0.285920000 -1.138921000 -4.679734000
C -3.088456000 -3.656586000 1.933700000
H -3.350095000 -4.626136000 2.366529000
C -1.805914000 2.886955000 1.571550000
C -1.084806000 3.617668000 0.614033000
H -0.743747000 4.611001000 0.909431000
46
 C 0.104035000 4.066172000 -1.552687000
H -0.327579000 4.107365000 -2.565402000
H 0.208382000 5.083447000 -1.150400000
H 1.108630000 3.615210000 -1.641127000
C -2.606278000 -3.579935000 0.633402000
H -2.492865000 -4.494171000 0.042220000
C -0.942630000 -2.800697000 -3.431183000
H -0.719073000 -3.579094000 -4.166145000
C -2.115976000 3.509652000 2.900566000
H -1.668018000 2.897324000 3.701273000
H -1.744578000 4.540530000 2.979241000
H -3.207269000 3.499003000 3.058029000

Cartesian coordinate of model IM1···II for 1·(4-NC5F4)2Te (in Å)

E = – 26626.9617691

Pt -2.039693000 -0.523526000 -0.077440000

O -1.592902000 -1.733165000 -1.610223000
O -1.807598000 -2.073261000 1.279287000
C -1.986979000 1.081244000 -1.202901000
N -2.244498000 0.851947000 1.348466000
C -1.864622000 1.159783000 -2.597599000
H -1.715759000 0.238073000 -3.167402000
C -2.272518000 2.156008000 0.937091000
C -2.170745000 2.307008000 -0.507239000
C -1.190083000 -3.152679000 1.000277000
C -1.885482000 2.383942000 -3.261667000
H -1.777173000 2.411164000 -4.350946000
C -0.993369000 -2.854208000 -1.484457000
C -0.483447000 -3.425190000 -2.771721000
C -0.894056000 -4.037624000 2.174761000
C -2.189160000 3.540784000 -1.171168000
H -2.316511000 4.473200000 -0.612332000
47
 C -2.300462000 0.565789000 2.659801000
H -2.246647000 -0.497853000 2.906604000
C -2.403995000 1.546072000 3.632852000
H -2.447406000 1.258661000 4.685290000
C -2.445778000 2.883376000 3.232258000
H -2.526370000 3.685107000 3.971679000
C -2.050535000 3.579563000 -2.552735000
H -2.066251000 4.537659000 -3.079533000
C -2.377600000 3.183441000 1.879312000
H -2.396584000 4.219492000 1.536291000
C -0.784154000 -3.554693000 -0.285136000
H -0.245809000 -4.500456000 -0.358857000
Te 1.099163000 -0.170173000 -0.211812000
F 2.932299000 2.606211000 -0.272985000
F 5.581460000 2.927229000 0.062988000
F 3.619922000 -2.044509000 0.306078000
F 6.251300000 -1.500424000 0.616618000
N 5.906054000 0.712569000 0.339794000
H 0.782160000 1.382830000 -0.487783000
C 5.405371000 -0.500095000 0.395434000
C 3.700234000 1.533691000 -0.054666000
C 5.071512000 1.701706000 0.119752000
C 3.148996000 0.254898000 0.002384000
C 4.052706000 -0.780106000 0.234919000
H -1.254887000 -3.325959000 -3.551189000
H -0.177646000 -4.475968000 -2.675102000
H 0.387503000 -2.826729000 -3.093213000
H -1.817142000 -4.196308000 2.755575000
H -0.175264000 -3.524004000 2.836634000
H -0.473396000 -5.007882000 1.876880000

Cartesian coordinate of model IM1···IITB for 2·(4-NC5F4)2Te (in Å)

E = – 26862.6812354

48
Pt -1.942000000 0.449000000 -0.281000000
O -1.427000000 1.894000000 1.004000000
O -0.925000000 1.400000000 -1.815000000
C -2.600000000 -0.728000000 1.143000000
N -2.309000000 -1.175000000 -1.376000000
C -2.758000000 -0.438000000 2.506000000
H -2.440000000 0.540000000 2.878000000
C -2.814000000 -2.257000000 -0.709000000
C -3.022000000 -2.014000000 0.711000000
C 0.036000000 2.206000000 -1.590000000
C -3.275000000 -1.377000000 3.395000000
H -3.379000000 -1.120000000 4.455000000
C -0.443000000 2.693000000 0.828000000
C -0.072000000 3.478000000 2.084000000
C 0.954000000 2.433000000 -2.791000000
C -3.541000000 -2.963000000 1.602000000
H -3.847000000 -3.952000000 1.248000000
C -2.042000000 -1.266000000 -2.689000000
H -1.622000000 -0.363000000 -3.140000000
C -2.269000000 -2.421000000 -3.418000000
H -2.035000000 -2.440000000 -4.484000000
C -2.791000000 -3.535000000 -2.758000000
H -2.983000000 -4.466000000 -3.300000000
C -3.672000000 -2.642000000 2.947000000
H -4.079000000 -3.375000000 3.649000000
C -3.061000000 -3.448000000 -1.400000000
H -3.461000000 -4.305000000 -0.855000000
C 0.283000000 2.847000000 -0.363000000
H 1.129000000 3.525000000 -0.328000000
C -1.350000000 4.108000000 2.649000000
H -1.775000000 4.844000000 1.944000000
H -1.123000000 4.632000000 3.592000000
H -2.114000000 3.342000000 2.845000000
C 2.053000000 3.461000000 -2.534000000
H 1.642000000 4.452000000 -2.281000000
H 2.662000000 3.579000000 -3.446000000
H 2.731000000 3.144000000 -1.725000000
C 0.496000000 2.465000000 3.091000000
H -0.235000000 1.671000000 3.310000000
H 0.752000000 2.978000000 4.034000000
H 1.408000000 1.984000000 2.700000000
C 1.603000000 1.077000000 -3.111000000
H 2.197000000 0.712000000 -2.257000000
H 2.271000000 1.175000000 -3.983000000
H 0.840000000 0.316000000 -3.336000000
C 0.965000000 4.570000000 1.833000000
H 1.934000000 4.157000000 1.508000000
H 1.145000000 5.123000000 2.770000000
H 0.623000000 5.297000000 1.077000000
C 0.091000000 2.890000000 -3.973000000
H -0.712000000 2.166000000 -4.179000000
H 0.714000000 2.992000000 -4.877000000
49
 H -0.375000000 3.869000000 -3.768000000
Te 0.879000000 -0.590000000 0.574000000
F 2.429000000 -3.557000000 0.546000000
F 5.060000000 -4.101000000 0.360000000
F 3.568000000 1.039000000 0.428000000
F 6.161000000 0.274000000 0.242000000
N 5.600000000 -1.912000000 0.301000000
H 0.354000000 -2.114000000 0.638000000
C 5.216000000 -0.656000000 0.320000000
C 3.306000000 -2.550000000 0.476000000
C 4.666000000 -2.832000000 0.378000000
C 2.879000000 -1.225000000 0.494000000
C 3.886000000 -0.264000000 0.419000000

4.5.2 Optimized geometries in CHCl3 solution

Cartesian coordinate of model I···IITB for 2·(4-NC5F4)2Te (in Å)

E = – 27506.7089557

Pt 1.956111000 0.582355000 -0.368054000

O 1.243168000 2.163086000 -1.369200000
O 1.927599000 1.657445000 1.394913000
C 1.762301000 -0.633927000 -1.899047000
N 2.639806000 -1.091788000 0.480344000
C 1.270113000 -0.342965000 -3.178757000
H 0.876035000 0.657719000 -3.378895000
C 2.719598000 -2.194032000 -0.324427000
C 2.245594000 -1.952186000 -1.681517000
C 1.274592000 2.740739000 1.563060000
C 1.227504000 -1.312737000 -4.179415000
H 0.823661000 -1.056896000 -5.164737000
C 0.752478000 3.224218000 -0.845804000
C 0.078472000 4.145559000 -1.860609000
C 1.070973000 3.125860000 3.027099000
C 2.200736000 -2.931644000 -2.681202000
H 2.558422000 -3.946789000 -2.482903000
50
C 3.037862000 -1.168890000 1.761251000
H 2.932799000 -0.251077000 2.344353000
C 3.529732000 -2.338694000 2.315841000
H 3.831610000 -2.351627000 3.365060000
C 3.616034000 -3.476218000 1.510760000
H 3.992303000 -4.419204000 1.916425000
C 1.691713000 -2.610425000 -3.935254000
H 1.651405000 -3.369672000 -4.721504000
C 3.210262000 -3.398359000 0.184939000
H 3.258917000 -4.274224000 -0.464698000
C 0.734812000 3.522411000 0.524388000
H 0.232259000 4.440284000 0.813047000
C 0.971431000 4.255425000 -3.100712000
H 1.946220000 4.708891000 -2.850592000
H 0.483019000 4.894071000 -3.855780000
H 1.159629000 3.268669000 -3.549158000
C 0.453178000 4.508930000 3.214611000
H 1.067013000 5.302523000 2.756149000
H 0.376854000 4.728936000 4.292617000
H -0.564987000 4.570158000 2.796007000
C -1.251733000 3.472103000 -2.238545000
H -1.086524000 2.465863000 -2.655200000
H -1.777730000 4.079334000 -2.995429000
H -1.914269000 3.376929000 -1.360376000
C 0.128880000 2.064956000 3.618369000
H -0.822820000 2.019740000 3.062550000
H -0.096922000 2.308653000 4.670871000
H 0.586044000 1.064584000 3.582473000
C -0.196333000 5.543562000 -1.310729000
H -0.922828000 5.533400000 -0.481794000
H -0.624747000 6.170799000 -2.110275000
H 0.726430000 6.034287000 -0.957687000
C 2.425346000 3.074441000 3.742018000
H 2.895622000 2.084840000 3.635129000
H 2.289915000 3.280114000 4.817458000
H 3.119253000 3.831065000 3.335973000
Te -1.102858000 0.342002000 -0.104834000
F -2.929887000 -0.913252000 2.354469000
F -5.586576000 -1.323799000 2.540595000
F -3.705010000 0.779870000 -2.007973000
F -6.324954000 0.312749000 -1.597474000
F -1.297840000 -2.311588000 -1.920874000
F -0.029737000 -1.271391000 2.525536000
F 0.519637000 -3.886100000 2.856789000
N -5.936160000 -0.505314000 0.468102000
F -0.619459000 -4.860287000 -1.395777000
C -0.680295000 -1.661041000 0.276233000
C -5.454661000 0.013089000 -0.636378000
C -3.714132000 -0.595906000 1.321580000
C -0.836499000 -2.623447000 -0.715731000
C -5.086128000 -0.804569000 1.421801000
C -3.182874000 -0.059109000 0.153003000
51
 C -0.212031000 -2.107172000 1.508393000
C -4.099119000 0.251898000 -0.846998000
C 0.080183000 -3.457489000 1.676909000
N -0.052367000 -4.350420000 0.725316000
C -0.498872000 -3.945479000 -0.438320000

Cartesian coordinate of 2 (in Å)

E = – 19431.2427422

Pt -0.410774000 0.007576000 -0.261412000

O 0.967867000 1.451239000 -0.223736000
O 1.052650000 -1.443474000 -0.221283000
C -1.890265000 1.267607000 -0.014110000
N -1.891206000 -1.303849000 -0.047327000
C -1.859722000 2.672925000 -0.040553000
H -0.894501000 3.179674000 -0.138821000
C -3.146303000 -0.788958000 0.136137000
C -3.176134000 0.668555000 0.115194000
C 2.291790000 -1.224387000 -0.007901000
C -3.018571000 3.436099000 0.094298000
H -2.952458000 4.529719000 0.078733000
C 2.216673000 1.286210000 0.005727000
C 2.972004000 2.605217000 0.169386000
C 3.132462000 -2.495484000 0.123214000
C -4.344476000 1.429992000 0.249504000
H -5.317718000 0.939746000 0.356184000
C -1.717690000 -2.637587000 -0.032082000
H -0.689122000 -2.977703000 -0.175643000
C -2.763876000 -3.526512000 0.153509000
H -2.563381000 -4.600280000 0.154852000
C -4.051339000 -3.017510000 0.336880000
H -4.901769000 -3.688801000 0.487055000
C -4.267563000 2.818848000 0.235455000
H -5.175508000 3.420980000 0.336157000
C -4.236662000 -1.641582000 0.328283000
H -5.229473000 -1.211654000 0.476736000
C 2.875489000 0.050391000 0.103175000
H 3.942944000 0.083589000 0.297163000
C 2.721240000 3.449444000 -1.086934000
H 3.121968000 2.951629000 -1.987269000
52
 H 3.222627000 4.427467000 -0.988102000
H 1.645173000 3.623461000 -1.241453000
C 4.612856000 -2.226293000 0.380804000
H 5.079477000 -1.655693000 -0.439454000
H 5.149181000 -3.186896000 0.461291000
H 4.776556000 -1.677382000 1.323252000
C 2.383187000 3.316565000 1.396252000
H 1.302129000 3.490033000 1.275730000
H 2.878528000 4.292192000 1.540658000
H 2.533924000 2.718990000 2.312267000
C 2.556905000 -3.310340000 1.289541000
H 2.636860000 -2.754745000 2.240225000
H 3.113652000 -4.256714000 1.400547000
H 1.494903000 -3.550670000 1.123500000
C 4.475547000 2.426912000 0.363417000
H 4.712631000 1.858708000 1.278377000
H 4.949135000 3.418386000 0.460727000
H 4.946595000 1.917919000 -0.494192000
C 2.982054000 -3.285261000 -1.183981000
H 1.925040000 -3.516060000 -1.390151000
H 3.539565000 -4.235360000 -1.117051000
H 3.382106000 -2.715773000 -2.041018000

Cartesian coordinate of (4-NC5F4)2Te (in Å)

E = – 8075.44657187

Te 0.000018000 1.747566000 0.000005000

F 2.924493000 1.501660000 1.291207000
F 0.304075000 -0.981378000 -1.780330000
F 2.366587000 -2.702038000 -1.971512000
F -0.304158000 -0.981287000 1.780456000
F -2.924406000 1.501633000 -1.291325000
F 4.870177000 -0.329114000 0.931656000
F -4.870125000 -0.329104000 -0.931782000
F -2.366697000 -2.701915000 1.971618000
N -3.604779000 -1.502517000 0.518556000
N 3.604751000 -1.502582000 -0.518567000
53
 C 1.517261000 0.339215000 -0.224062000
C -1.517253000 0.339243000 0.224062000
C 1.409688000 -0.760720000 -1.072698000
C -3.725364000 -0.465030000 -0.273537000
C -1.409730000 -0.760655000 1.072753000
C 3.725383000 -0.465060000 0.273473000
C 2.476819000 -1.648765000 -1.170947000
C 2.721717000 0.481563000 0.461015000
C -2.476879000 -1.648678000 1.170999000
C -2.721681000 0.481578000 -0.461069000

4.5.3 X-ray geometries

Cartesian coordinate of model I···II for 1·(4-NC5F4)2Se (in Å)

E = – 22913.8453090

Se 0.971632000 -1.034293000 0.103454000

F 1.226097000 0.941804000 -2.302892000
F 3.112665000 -0.978210000 2.388282000
F 1.051252000 1.106412000 2.426195000
F 5.655503000 -1.507888000 -2.278712000
F 1.685175000 3.576972000 -2.277044000
F 2.968972000 -1.494862000 -2.324249000
F 1.616360000 3.731124000 2.229719000
F 5.783686000 -1.040879000 2.197430000
N 1.632385000 3.642635000 -0.028362000
N 5.712736000 -1.266746000 -0.035604000
C 1.269207000 1.575862000 -1.119567000
C 1.133275000 0.887666000 0.064886000
C 1.204722000 1.650478000 1.216746000
C 3.673239000 -1.139267000 1.194856000
C 5.051652000 -1.154900000 1.084460000
C 1.519338000 2.934064000 -1.104107000
C 4.978051000 -1.389110000 -1.139334000
C 3.603040000 -1.378917000 -1.152245000
54
C 1.477173000 3.000186000 1.105937000
C 2.913930000 -1.221969000 0.042820000
Pt -2.165040000 0.142527000 -0.025366000
O -1.972254000 1.465431000 -1.611459000
O -2.039955000 1.629658000 1.342174000
N -2.251911000 -1.440428000 -1.226151000
C -2.272109000 -1.272858000 1.358086000
C -2.314288000 -2.660250000 -0.593242000
C -2.325128000 -2.574128000 0.846444000
C -2.232396000 -1.374038000 -2.586686000
H -2.191130000 -0.524363000 -3.011800000
C -1.822639000 2.719731000 -1.474481000
C -2.330312000 -2.184589000 3.587455000
H -2.339896000 -2.046793000 4.527840000
C -2.278621000 -1.086066000 2.720210000
H -2.248258000 -0.205873000 3.074932000
C -2.364009000 -3.828897000 -1.355080000
H -2.414109000 -4.674193000 -0.925407000
C -2.268453000 -2.523976000 -3.358883000
H -2.245891000 -2.465813000 -4.307036000
C -2.369319000 -3.471560000 3.076292000
H -2.397082000 -4.217279000 3.663531000
C -1.866064000 2.865924000 1.038773000
C -1.773999000 3.406053000 -0.252987000
H -1.666380000 4.347776000 -0.307135000
C -1.677478000 3.483550000 -2.752294000
H -2.518321000 3.442199000 -3.254666000
H -1.462386000 4.417629000 -2.552223000
H -0.958139000 3.088702000 -3.287798000
C -2.367442000 -3.667113000 1.712504000
H -2.393153000 -4.550386000 1.361639000
C -2.337954000 -3.753197000 -2.740183000
H -2.368316000 -4.547623000 -3.261079000
C -1.757850000 3.779696000 2.233361000
H -1.033327000 3.471272000 2.815356000
H -1.568592000 4.691446000 1.929243000
H -2.602941000 3.768734000 2.729824000

Cartesian coordinate of model I···II for 1·(4-NC5F4)2Te (in Å)

E = – 27270.6596507

55
Pt -2.207395000 0.339723000 -0.026275000
O -1.884757000 1.785811000 1.337740000
O -1.846958000 1.639225000 -1.606642000
N -2.520230000 -1.209232000 -1.233246000
C -2.504837000 -1.051270000 1.356458000
C -2.501429000 -1.155135000 -2.586446000
H -2.363973000 -0.332877000 -3.001959000
C -2.749101000 -2.411696000 -0.610689000
C -2.453052000 -0.873381000 2.731977000
H -2.295949000 -0.027889000 3.086541000
C -2.677446000 -2.270802000 -3.368858000
H -2.647095000 -2.211282000 -4.296372000
C -2.635985000 -1.967549000 3.581220000
H -2.615794000 -1.839592000 4.502118000
C -2.903614000 -3.493373000 -2.740882000
H -3.033716000 -4.260123000 -3.251865000
C -2.895709000 -3.426808000 1.699602000
H -3.037965000 -4.276225000 1.349639000
C -1.562583000 2.998803000 1.052052000
C -2.729368000 -2.335228000 0.852354000
C -2.844099000 -3.231029000 3.076821000
H -2.951285000 -3.951974000 3.653869000
C -1.542082000 2.856219000 -1.465832000
C -2.937310000 -3.567983000 -1.372769000
H -3.084513000 -4.385689000 -0.953220000
C -1.321950000 3.861070000 2.256495000
H -2.121174000 3.899906000 2.787641000
H -1.082197000 4.746920000 1.972216000
H -0.608541000 3.488277000 2.779374000
C -1.304552000 3.609218000 -2.752931000
H -0.664164000 3.134193000 -3.288229000
H -0.968349000 4.485428000 -2.552540000
H -2.130777000 3.686194000 -3.235454000
C -1.398952000 3.532810000 -0.227986000
H -1.170328000 4.433714000 -0.273143000
Te 0.710365000 -1.093061000 0.112438000
56
F 1.204477000 1.220261000 2.421041000
F 1.304225000 1.019567000 -2.308432000
F 2.089959000 3.571012000 -2.288823000
F 3.086356000 -1.217124000 2.371475000
F 2.874088000 -1.728678000 -2.332773000
F 2.071242000 3.752646000 2.213802000
F 5.554105000 -1.909755000 -2.313114000
F 5.745969000 -1.450839000 2.167798000
N 5.633507000 -1.691249000 -0.073219000
N 2.070151000 3.656167000 -0.037530000
C 1.211911000 0.976023000 0.065049000
C 2.849109000 -1.454097000 0.024431000
C 1.447139000 1.634855000 -1.131314000
C 4.904046000 -1.753649000 -1.160481000
C 3.635500000 -1.406170000 1.166888000
C 1.836062000 3.045887000 1.090963000
C 1.851964000 2.949008000 -1.123831000
C 1.409048000 1.736945000 1.206887000
C 5.001860000 -1.525963000 1.060005000
C 3.517027000 -1.652057000 -1.161763000

Cartesian coordinate of model I···IITB for 1·(4-NC5F4)2Te (in Å)

E = – 27506.3150380

Pt -1.578048000 -1.144379000 0.211308000

O -2.413412000 0.230344000 1.488711000
O -2.566274000 -0.348101000 -1.371510000
C -0.539737000 -2.064834000 1.640777000
N -0.775847000 -2.583972000 -0.896239000
C -0.461772000 -1.674636000 2.945341000
H -0.940957000 -0.904585000 3.230645000
C 0.006491000 -3.496682000 -0.194711000
C 0.163870000 -3.184469000 1.222837000
57
C -3.186886000 0.773348000 -1.352456000
C 0.296362000 -2.372257000 3.853663000
H 0.336190000 -2.087567000 4.758554000
C -3.078482000 1.248508000 1.106117000
C -3.443222000 2.233427000 2.227566000
C -3.677568000 1.197193000 -2.733015000
C 0.936352000 -3.903975000 2.133712000
H 1.413438000 -4.673666000 1.848599000
C -0.971232000 -2.768492000 -2.236798000
H -1.496471000 -2.144505000 -2.723144000
C -0.413799000 -3.854459000 -2.894780000
H -0.550968000 -3.963943000 -3.828790000
C 0.339534000 -4.779304000 -2.195223000
H 0.706412000 -5.532640000 -2.643342000
C 1.006494000 -3.494273000 3.444677000
H 1.536423000 -3.977185000 4.067634000
C 0.559640000 -4.602550000 -0.843396000
H 1.083794000 -5.228459000 -0.359082000
C -3.425610000 1.548589000 -0.215161000
H -3.876474000 2.373102000 -0.354208000
C -3.626115000 1.487071000 3.557263000
H -4.397631000 0.887970000 3.491355000
H -3.775782000 2.135200000 4.277065000
H -2.819695000 0.963998000 3.751062000
C -4.287626000 2.604801000 -2.764493000
H -5.090130000 2.625303000 -2.202069000
H -4.528500000 2.836625000 -3.685695000
H -3.634614000 3.252066000 -2.425146000
C -2.250748000 3.198068000 2.339486000
H -1.442972000 2.692616000 2.568306000
H -2.431779000 3.859777000 3.038539000
H -2.118657000 3.654782000 1.482247000
C -2.454569000 1.229325000 -3.672238000
H -1.795597000 1.868537000 -3.327867000
H -2.737799000 1.503401000 -4.569293000
H -2.052444000 0.336797000 -3.714782000
C -4.713552000 3.030352000 1.936008000
H -4.555624000 3.630197000 1.176602000
H -4.955110000 3.558322000 2.724921000
H -5.442924000 2.413257000 1.719044000
C -4.693061000 0.184945000 -3.200474000
H -4.290868000 -0.708384000 -3.192544000
H -4.979650000 0.406775000 -4.112170000
H -5.468917000 0.199472000 -2.601453000
Te 0.525705000 1.048879000 -0.125102000
F 3.549884000 1.311134000 -1.691558000
F 5.255690000 3.370457000 -1.818553000
F 0.797222000 4.005918000 1.070503000
F 2.625046000 5.959801000 0.764435000
F 2.413101000 -0.154298000 2.233536000
F 1.725670000 -1.046736000 -2.346470000
F 3.482798000 -3.078631000 -2.074227000
58
N 3.945934000 4.654401000 -0.504901000
F 4.116132000 -2.207136000 2.296559000
C 1.964688000 -0.514325000 -0.074983000
C 2.845699000 4.771706000 0.186244000
C 3.259736000 2.442541000 -1.015850000
C 2.619831000 -0.832209000 1.117241000
C 4.142672000 3.495614000 -1.089181000
C 2.093228000 2.545162000 -0.280888000
C 2.270925000 -1.288403000 -1.156423000
C 1.912281000 3.767717000 0.337110000
C 3.214740000 -2.353125000 -0.996176000
N 3.794846000 -2.617603000 0.141618000
C 3.500014000 -1.896000000 1.134757000

Cartesian coordinate of model I···III for 1·(4-NC5F4)2Se (in Å)

E = – 22913.8386506

Se -2.887923000 -0.048305000 1.433551000

F -4.414124000 -2.309104000 -0.089507000
F -1.491722000 2.240983000 -0.184285000
F -4.397653000 2.419336000 0.162508000
F 0.239700000 -2.444340000 -2.075670000
F -6.202231000 -2.096831000 -2.067675000
F -1.426551000 -2.496598000 0.031595000
F -6.124195000 2.409406000 -1.902926000
F 0.191345000 2.053903000 -2.259615000
N -6.165805000 0.150745000 -1.964021000
N 0.205566000 -0.189677000 -2.166696000
C -4.822719000 -1.084031000 -0.458822000
C -4.301753000 0.048740000 0.124655000
C -4.795833000 1.251554000 -0.347458000
C -1.084024000 1.040812000 -0.581551000
C -0.229233000 0.933566000 -1.663348000
C -5.735900000 -0.972452000 -1.488951000
C -0.209589000 -1.301392000 -1.562799000
59
C -1.064619000 -1.317520000 -0.485956000
C -5.695366000 1.236645000 -1.395712000
C -1.548112000 -0.116374000 0.015209000
Pt 2.218989000 0.021940000 0.687959000
O 1.255529000 -1.533165000 1.673613000
O 1.194501000 1.428672000 1.723443000
N 3.324130000 -1.212019000 -0.430274000
C 3.276393000 1.379719000 -0.300968000
C 3.197280000 -2.547657000 -0.444074000
H 2.503477000 -2.950922000 0.065892000
C 4.260771000 0.847883000 -1.126477000
C 5.163490000 -1.392736000 -1.958102000
H 5.834173000 -0.976113000 -2.485734000
C 4.277931000 -0.605996000 -1.193428000
C 4.053451000 -3.361251000 -1.182668000
H 3.957286000 -4.305357000 -1.168125000
C 5.012629000 3.063624000 -1.703870000
H 5.609453000 3.637361000 -2.167174000
C 0.326648000 1.166098000 2.628162000
C 3.133009000 2.755291000 -0.214362000
H 2.447150000 3.124678000 0.327727000
C -0.081905000 -0.106502000 3.053360000
H -0.753725000 -0.132293000 3.726590000
C 5.144819000 1.689359000 -1.806538000
H 5.838909000 1.317758000 -2.337297000
C 5.052260000 -2.760001000 -1.940971000
H 5.655775000 -3.294497000 -2.445516000
C -0.283723000 2.371127000 3.268880000
H -0.096956000 2.358203000 4.231202000
H -1.253659000 2.361007000 3.125050000
H 0.097780000 3.179925000 2.872548000
C 3.991735000 3.599019000 -0.916189000
H 3.883324000 4.540892000 -0.857996000
C 0.394354000 -1.349743000 2.595215000
C -0.151869000 -2.591313000 3.226603000
H 0.180021000 -3.377234000 2.743360000
H -1.131117000 -2.573111000 3.187138000
H 0.136958000 -2.636303000 4.162437000

Cartesian coordinate of model I···III for 1·(4-NC5F4)2Te (in Å)

E = – 27270.6493978

60
Te -2.736195000 -0.154064000 1.477262000
F -4.296353000 2.422738000 0.116657000
F -4.294872000 -2.277231000 -0.456430000
F -6.002509000 -1.919362000 -2.477208000
F -1.232807000 2.263171000 -0.155274000
F -1.140313000 -2.470083000 -0.296877000
F -5.954568000 2.560634000 -1.991146000
F 0.471883000 -2.253746000 -2.434561000
F 0.401996000 2.250566000 -2.274981000
N 0.437385000 -0.005029000 -2.335323000
N -5.979452000 0.319003000 -2.221950000
C -4.197829000 0.062483000 -0.056242000
C -1.273137000 -0.107509000 -0.125739000
C -4.677277000 -1.032979000 -0.756790000
C 0.039976000 -1.149198000 -1.830556000
C -0.831608000 1.093197000 -0.663579000
C -5.544424000 1.354012000 -1.556348000
C -5.556871000 -0.851237000 -1.798049000
C -4.674299000 1.291851000 -0.484369000
C 0.007887000 1.084690000 -1.753483000
C -0.799000000 -1.250310000 -0.727036000
Pt 2.308878000 -0.033253000 0.709655000
O 1.328397000 1.290065000 1.859604000
O 1.355647000 -1.658733000 1.607200000
N 3.371240000 -1.170124000 -0.532940000
C 4.042836000 -3.260398000 -1.493589000
H 3.931803000 -4.182392000 -1.558028000
C 3.234133000 -2.505528000 -0.648648000
H 2.576678000 -2.936860000 -0.150301000
C 4.309137000 -0.528384000 -1.285260000
C 3.328672000 1.398839000 -0.198439000
C 3.190110000 2.767400000 -0.008110000
H 2.534734000 3.094786000 0.565218000
C 0.453049000 0.966984000 2.746745000
61
C 5.141995000 -1.233647000 -2.156612000
H 5.771235000 -0.783912000 -2.673993000
C 4.286307000 0.924810000 -1.101973000
C 5.158300000 1.826383000 -1.765138000
H 5.807047000 1.508458000 -2.348494000
C -0.151546000 2.130325000 3.477707000
H 0.168690000 2.950291000 3.096857000
H -1.107951000 2.093422000 3.403064000
H 0.097531000 2.089159000 4.404282000
C 4.039615000 3.651603000 -0.677483000
H 3.940493000 4.567880000 -0.550497000
C 5.032321000 3.180285000 -1.533134000
H 5.609973000 3.777492000 -1.949779000
C 0.506657000 -1.550034000 2.544403000
C 5.020538000 -2.607660000 -2.239013000
H 5.590053000 -3.094631000 -2.790749000
C 0.041523000 -0.332525000 3.083479000
H -0.615495000 -0.398047000 3.738669000
C -0.041504000 -2.827832000 3.105940000
H 0.431643000 -3.054020000 3.909468000
H -0.974581000 -2.715868000 3.304414000
H 0.065726000 -3.532256000 2.462421000

Cartesian coordinate of model IM1···II for 1·(4-NC5F4)2Se (in Å)

E = – 22269.8309992

Se 1.361389000 -0.217298000 0.095092000

F 3.448768000 0.203294000 2.390813000
F 6.032749000 0.392087000 -2.279875000
F 3.403295000 -0.157964000 -2.337351000
F 6.073187000 0.710096000 2.211152000
N 6.044991000 0.557109000 -0.028348000
C 4.027588000 0.207378000 1.195213000

62
 C 5.377919000 0.485653000 1.090985000
C 5.348676000 0.323643000 -1.139544000
C 4.002430000 0.045731000 -1.159312000
C 3.299467000 0.010200000 0.037107000
H 1.184951000 1.225949000 -0.046594000
Pt -1.951422000 0.263858000 -0.004680000
O -2.045166000 1.655020000 -1.539476000
O -2.137967000 1.692340000 1.417590000
N -1.707396000 -1.256386000 -1.263192000
C -1.754836000 -1.193137000 1.325983000
C -1.510293000 -2.485094000 -0.675831000
C -1.535124000 -2.456418000 0.766247000
C -1.705959000 -1.137218000 -2.619832000
H -1.844867000 -0.282373000 -3.013301000
C -2.162677000 2.907000000 -1.355708000
C -1.613711000 -2.178533000 3.520061000
H -1.648900000 -2.080278000 4.464344000
C -1.796159000 -1.062156000 2.693364000
H -1.950593000 -0.208644000 3.080884000
C -1.315791000 -3.608508000 -1.480155000
H -1.185877000 -4.461326000 -1.082686000
C -1.502357000 -2.239642000 -3.434085000
H -1.494293000 -2.142768000 -4.379787000
C -1.382924000 -3.424867000 2.961385000
H -1.251685000 -4.181185000 3.520153000
C -2.228170000 2.947554000 1.160384000
C -2.255658000 3.542593000 -0.109812000
H -2.348413000 4.487082000 -0.128973000
C -2.184153000 3.730948000 -2.604197000
H -2.999711000 3.533159000 -3.111361000
H -2.170046000 4.682173000 -2.368263000
H -1.399745000 3.516110000 -3.150327000
C -1.343639000 -3.564830000 1.590975000
H -1.184217000 -4.420377000 1.207452000
C -1.310288000 -3.478281000 -2.861758000
H -1.174341000 -4.241212000 -3.411013000
C -2.311082000 3.819159000 2.389013000
H -1.536219000 3.648919000 2.963019000
H -2.318680000 4.761038000 2.118901000
H -3.133344000 3.612330000 2.879821000

Cartesian coordinate of model IM1···II for 1·(4-NC5F4)2Te (in Å)

E = – 26626.6282137

63
Pt 6.988000000 5.599000000 9.794000000
O 8.431000000 4.138000000 9.825000000
O 6.068000000 4.795000000 11.413000000
C 7.742000000 6.521000000 8.197000000
N 5.606000000 7.011000000 9.595000000
C 8.904000000 6.192000000 7.562000000
H 9.417000000 5.458000000 7.881000000
C 5.779000000 7.852000000 8.500000000
C 6.996000000 7.595000000 7.736000000
C 6.575000000 3.884000000 12.160000000
C 9.346000000 6.902000000 6.473000000
H 10.156000000 6.657000000 6.042000000
C 8.584000000 3.305000000 10.777000000
C 9.843000000 2.431000000 10.668000000
C 5.734000000 3.607000000 13.402000000
C 7.432000000 8.325000000 6.630000000
H 6.918000000 9.057000000 6.311000000
C 4.509000000 7.178000000 10.394000000
H 4.389000000 6.613000000 11.149000000
C 3.569000000 8.159000000 10.118000000
H 2.816000000 8.269000000 10.688000000
C 3.723000000 8.978000000 9.013000000
H 3.069000000 9.638000000 8.814000000
C 8.607000000 7.982000000 6.005000000
H 8.912000000 8.479000000 5.255000000
C 4.831000000 8.833000000 8.203000000
H 4.948000000 9.398000000 7.448000000
C 7.756000000 3.185000000 11.898000000
H 8.026000000 2.555000000 12.555000000
C 10.199000000 2.187000000 9.194000000
H 9.491000000 1.659000000 8.771000000
H 11.048000000 1.700000000 9.141000000
H 10.287000000 3.048000000 8.734000000
C 6.394000000 2.634000000 14.388000000
H 6.497000000 1.758000000 13.961000000
H 5.831000000 2.544000000 15.185000000
64
 H 7.274000000 2.977000000 14.647000000
C 10.968000000 3.233000000 11.343000000
H 11.091000000 4.083000000 10.870000000
H 11.799000000 2.717000000 11.312000000
H 10.727000000 3.411000000 12.277000000
C 5.561000000 4.942000000 14.154000000
H 6.442000000 5.292000000 14.404000000
H 5.026000000 4.796000000 14.962000000
H 5.106000000 5.587000000 13.574000000
C 9.696000000 1.079000000 11.366000000
H 9.623000000 1.218000000 12.334000000
H 10.481000000 0.527000000 11.172000000
H 8.890000000 0.629000000 11.038000000
C 4.401000000 3.061000000 12.953000000
H 3.980000000 3.696000000 12.336000000
H 3.822000000 2.930000000 13.734000000
H 4.536000000 2.204000000 12.498000000
Te 8.926000000 6.988000000 11.708000000
F 9.127000000 10.070000000 13.168000000
F 10.977000000 11.082000000 14.817000000
F 11.728000000 6.112000000 12.983000000
F 13.434000000 7.308000000 14.690000000
N 12.215000000 9.198000000 14.730000000
H 8.571000000 8.408000000 10.864000000
C 12.361000000 7.988000000 14.265000000
C 10.204000000 9.320000000 13.480000000
C 11.148000000 9.849000000 14.329000000
C 10.346000000 8.043000000 12.969000000
C 11.482000000 7.380000000 13.393000000

Cartesian coordinate of model IM1···IITB for 2·(4-NC5F4)2Te (in Å)

E = – 26862.2891064

Pt 6.988000000 5.599000000 9.794000000

O 8.431000000 4.138000000 9.825000000
O 6.068000000 4.795000000 11.413000000
65
C 7.742000000 6.521000000 8.197000000
N 5.606000000 7.011000000 9.595000000
C 8.904000000 6.192000000 7.562000000
H 9.417000000 5.458000000 7.881000000
C 5.779000000 7.852000000 8.500000000
C 6.996000000 7.595000000 7.736000000
C 6.575000000 3.884000000 12.160000000
C 9.346000000 6.902000000 6.473000000
H 10.156000000 6.657000000 6.042000000
C 8.584000000 3.305000000 10.777000000
C 9.843000000 2.431000000 10.668000000
C 5.734000000 3.607000000 13.402000000
C 7.432000000 8.325000000 6.630000000
H 6.918000000 9.057000000 6.311000000
C 4.509000000 7.178000000 10.394000000
H 4.389000000 6.613000000 11.149000000
C 3.569000000 8.159000000 10.118000000
H 2.816000000 8.269000000 10.688000000
C 3.723000000 8.978000000 9.013000000
H 3.069000000 9.638000000 8.814000000
C 8.607000000 7.982000000 6.005000000
H 8.912000000 8.479000000 5.255000000
C 4.831000000 8.833000000 8.203000000
H 4.948000000 9.398000000 7.448000000
C 7.756000000 3.185000000 11.898000000
H 8.026000000 2.555000000 12.555000000
C 10.199000000 2.187000000 9.194000000
H 9.491000000 1.659000000 8.771000000
H 11.048000000 1.700000000 9.141000000
H 10.287000000 3.048000000 8.734000000
C 6.394000000 2.634000000 14.388000000
H 6.497000000 1.758000000 13.961000000
H 5.831000000 2.544000000 15.185000000
H 7.274000000 2.977000000 14.647000000
C 10.968000000 3.233000000 11.343000000
H 11.091000000 4.083000000 10.870000000
H 11.799000000 2.717000000 11.312000000
H 10.727000000 3.411000000 12.277000000
C 5.561000000 4.942000000 14.154000000
H 6.442000000 5.292000000 14.404000000
H 5.026000000 4.796000000 14.962000000
H 5.106000000 5.587000000 13.574000000
C 9.696000000 1.079000000 11.366000000
H 9.623000000 1.218000000 12.334000000
H 10.481000000 0.527000000 11.172000000
H 8.890000000 0.629000000 11.038000000
C 4.401000000 3.061000000 12.953000000
H 3.980000000 3.696000000 12.336000000
H 3.822000000 2.930000000 13.734000000
H 4.536000000 2.204000000 12.498000000
Te 8.926000000 6.988000000 11.708000000
F 9.127000000 10.070000000 13.168000000
66
 F 10.977000000 11.082000000 14.817000000
F 11.728000000 6.112000000 12.983000000
F 13.434000000 7.308000000 14.690000000
N 12.215000000 9.198000000 14.730000000
H 8.571000000 8.408000000 10.864000000
C 12.361000000 7.988000000 14.265000000
C 10.204000000 9.320000000 13.480000000
C 11.148000000 9.849000000 14.329000000
C 10.346000000 8.043000000 12.969000000
C 11.482000000 7.380000000 13.393000000

Cartesian coordinate of model IM2···II for 1·(4-NC5F4)2Se (in Å)

E = – 19840.4742504

Pt 0.778928000 -0.032028000 0.653275000

O -0.566324000 1.350116000 1.232733000
O -0.518560000 -1.594369000 1.091219000
N 2.205408000 -1.257903000 0.008066000
C 2.111690000 1.332985000 0.109426000
C 2.127152000 -2.610047000 0.011682000
H 1.368252000 -3.015819000 0.368156000
C 3.331481000 -0.650073000 -0.490312000
C 1.959950000 2.710716000 0.181607000
H 1.183946000 3.075421000 0.542246000
C 3.127758000 -3.405245000 -0.492611000
H 3.045723000 -4.331536000 -0.491524000
C 2.974899000 3.546940000 -0.290080000
H 2.874379000 4.469150000 -0.224814000
C 4.268824000 -2.792129000 -1.004711000
H 4.962203000 -3.312061000 -1.343577000
C 4.285906000 1.648252000 -0.933216000
H 5.056670000 1.288367000 -1.308218000
C -1.748856000 1.080787000 1.663833000
C 3.282643000 0.813715000 -0.449422000
C 4.119657000 3.027839000 -0.850592000
H 4.781034000 3.596535000 -1.172152000
C -1.687116000 -1.437541000 1.542586000
C 4.372677000 -1.425513000 -1.007796000
H 5.133523000 -1.015834000 -1.353643000
67
 C -2.572023000 2.296796000 1.973367000
H -2.135429000 2.814469000 2.654383000
H -3.439490000 2.024555000 2.283866000
H -2.667990000 2.828512000 1.180020000
C -2.461789000 -2.713633000 1.769573000
H -2.450279000 -3.242058000 0.967747000
H -3.368488000 -2.499724000 1.999946000
H -2.058256000 -3.209564000 2.485544000
C -2.301756000 -0.191459000 1.825465000
H -3.171050000 -0.224679000 2.155863000
F -1.860221000 2.481219000 -1.610362000
F -1.834371000 -2.247441000 -1.849627000
F -4.373207000 -2.191683000 -1.025711000
F -4.433913000 2.311393000 -0.865733000
N -4.392923000 0.059606000 -0.940427000
C -1.705024000 0.123625000 -1.777904000
C -2.399769000 -1.062624000 -1.602352000
C -3.739722000 1.178448000 -1.089607000
C -3.707543000 -1.036519000 -1.178109000
C -2.421347000 1.275394000 -1.491597000
H -0.670249000 0.148864000 -2.116845000

Cartesian coordinate of model IM2···II for 1·(4-NC5F4)2Te (in Å)

E = – 19840.3913368

Pt 0.778928000 -0.032028000 0.653275000

O -0.566324000 1.350116000 1.232733000
O -0.518560000 -1.594369000 1.091219000
N 2.205408000 -1.257903000 0.008066000
C 2.111690000 1.332985000 0.109426000
C 2.127152000 -2.610047000 0.011682000
H 1.368252000 -3.015819000 0.368156000
C 3.331481000 -0.650073000 -0.490312000
C 1.959950000 2.710716000 0.181607000
H 1.183946000 3.075421000 0.542246000
C 3.127758000 -3.405245000 -0.492611000
H 3.045723000 -4.331536000 -0.491524000
C 2.974899000 3.546940000 -0.290080000
H 2.874379000 4.469150000 -0.224814000

68
 C 4.268824000 -2.792129000 -1.004711000
H 4.962203000 -3.312061000 -1.343577000
C 4.285906000 1.648252000 -0.933216000
H 5.056670000 1.288367000 -1.308218000
C -1.748856000 1.080787000 1.663833000
C 3.282643000 0.813715000 -0.449422000
C 4.119657000 3.027839000 -0.850592000
H 4.781034000 3.596535000 -1.172152000
C -1.687116000 -1.437541000 1.542586000
C 4.372677000 -1.425513000 -1.007796000
H 5.133523000 -1.015834000 -1.353643000
C -2.572023000 2.296796000 1.973367000
H -2.135429000 2.814469000 2.654383000
H -3.439490000 2.024555000 2.283866000
H -2.667990000 2.828512000 1.180020000
C -2.461789000 -2.713633000 1.769573000
H -2.450279000 -3.242058000 0.967747000
H -3.368488000 -2.499724000 1.999946000
H -2.058256000 -3.209564000 2.485544000
C -2.301756000 -0.191459000 1.825465000
H -3.171050000 -0.224679000 2.155863000
F -1.860221000 2.481219000 -1.610362000
F -1.834371000 -2.247441000 -1.849627000
F -4.373207000 -2.191683000 -1.025711000
F -4.433913000 2.311393000 -0.865733000
N -4.392923000 0.059606000 -0.940427000
C -1.705024000 0.123625000 -1.777904000
C -2.399769000 -1.062624000 -1.602352000
C -3.739722000 1.178448000 -1.089607000
C -3.707543000 -1.036519000 -1.178109000
C -2.421347000 1.275394000 -1.491597000
H -0.670249000 0.148864000 -2.116845000

Cartesian coordinate of model IM2···IITB for 2·(4-NC5F4)2Te (in Å)

E = – 20076.0379236

Pt 7.034000000 5.416000000 9.903000000

O 8.477000000 3.955000000 9.934000000
O 6.114000000 4.612000000 11.522000000
69
C 7.788000000 6.338000000 8.306000000
N 5.652000000 6.828000000 9.704000000
C 8.950000000 6.009000000 7.671000000
H 9.463000000 5.275000000 7.990000000
C 5.825000000 7.669000000 8.609000000
C 7.042000000 7.412000000 7.845000000
C 6.621000000 3.701000000 12.269000000
C 9.392000000 6.719000000 6.582000000
H 10.202000000 6.474000000 6.151000000
C 8.630000000 3.122000000 10.886000000
C 9.889000000 2.248000000 10.777000000
C 5.780000000 3.424000000 13.511000000
C 7.478000000 8.142000000 6.739000000
H 6.964000000 8.874000000 6.420000000
C 4.555000000 6.995000000 10.503000000
H 4.435000000 6.430000000 11.258000000
C 3.615000000 7.976000000 10.227000000
H 2.862000000 8.086000000 10.797000000
C 3.769000000 8.795000000 9.122000000
H 3.115000000 9.455000000 8.923000000
C 8.653000000 7.799000000 6.114000000
H 8.958000000 8.296000000 5.364000000
C 4.877000000 8.650000000 8.312000000
H 4.994000000 9.215000000 7.557000000
C 7.802000000 3.002000000 12.007000000
H 8.072000000 2.372000000 12.664000000
C 10.245000000 2.004000000 9.303000000
H 9.537000000 1.476000000 8.880000000
H 11.094000000 1.517000000 9.250000000
H 10.333000000 2.865000000 8.843000000
C 6.440000000 2.451000000 14.497000000
H 6.543000000 1.575000000 14.070000000
H 5.877000000 2.361000000 15.294000000
H 7.320000000 2.794000000 14.756000000
C 11.014000000 3.050000000 11.452000000
H 11.137000000 3.900000000 10.979000000
H 11.845000000 2.534000000 11.421000000
H 10.773000000 3.228000000 12.386000000
C 5.607000000 4.759000000 14.263000000
H 6.488000000 5.109000000 14.513000000
H 5.072000000 4.613000000 15.071000000
H 5.152000000 5.404000000 13.683000000
C 9.742000000 0.896000000 11.475000000
H 9.669000000 1.035000000 12.443000000
H 10.527000000 0.344000000 11.281000000
H 8.936000000 0.446000000 11.147000000
C 4.447000000 2.878000000 13.062000000
H 4.026000000 3.513000000 12.445000000
H 3.868000000 2.747000000 13.843000000
H 4.582000000 2.021000000 12.607000000
F 10.481000000 8.395000000 9.415000000
F 6.559000000 9.024000000 11.958000000
70
 F 6.077000000 11.195000000 10.426000000
F 9.825000000 10.568000000 8.012000000
C 8.525000000 8.591000000 10.755000000
C 9.366000000 9.032000000 9.730000000
C 7.407000000 9.341000000 10.982000000
C 7.175000000 10.496000000 10.168000000
N 7.986000000 10.863000000 9.215000000
C 9.015000000 10.159000000 9.013000000
H 8.749000000 7.700000000 11.340000000

Cartesian coordinate of model IM1···III for 1·(4-NC5F4)2Se (in Å)

E = – 22269.8223388

Se -3.045864000 -0.166015000 1.164792000

F -4.558851000 -2.322246000 -0.515473000
F -4.550729000 2.379074000 0.049598000
F -6.333826000 -1.980708000 -2.487495000
F -6.263376000 2.504220000 -2.023390000
N -6.301154000 0.254340000 -2.234419000
C -4.966470000 -1.075523000 -0.805565000
C -4.450516000 0.016300000 -0.144616000
C -4.943860000 1.247578000 -0.538870000
C -5.872856000 -0.896921000 -1.831657000
C -5.836136000 1.301072000 -1.592421000
H -2.073032000 -0.152124000 0.076257000
Pt 2.086008000 -0.040464000 0.437641000
O 1.118214000 -1.659232000 1.311658000
O 1.052691000 1.292765000 1.557587000
N 3.200454000 -1.196949000 -0.751808000
C 3.147901000 1.380269000 -0.451333000
C 3.075123000 -2.528415000 -0.855767000
H 2.379007000 -2.965692000 -0.377811000
C 4.138265000 0.906113000 -1.303852000
C 5.049452000 -1.273565000 -2.276702000
H 5.723606000 -0.822359000 -2.770771000
C 4.158122000 -0.540551000 -1.466969000
71
 C 3.937396000 -3.290337000 -1.640458000
H 3.842804000 -4.233567000 -1.688902000
C 4.890698000 3.155638000 -1.727968000
H 5.489615000 3.759119000 -2.148846000
C 0.178496000 0.970055000 2.436622000
C 3.002033000 2.746948000 -0.275221000
H 2.311471000 3.079013000 0.285648000
C -0.230994000 -0.328714000 2.773796000
H -0.906708000 -0.399226000 3.439329000
C 5.025610000 1.790887000 -1.921116000
H 5.724141000 1.455873000 -2.469952000
C 4.941053000 -2.639905000 -2.350475000
H 5.548595000 -3.138889000 -2.884888000
C -0.437713000 2.129769000 3.151350000
H -0.257190000 2.052695000 4.112142000
H -1.406324000 2.127882000 3.000833000
H -0.055081000 2.963521000 2.812980000
C 3.863431000 3.636630000 -0.913573000
H 3.753838000 4.572090000 -0.793629000
C 0.250764000 -1.537746000 2.237920000
C -0.298270000 -2.818722000 2.781661000
H 0.038342000 -3.570777000 2.249564000
H -1.277163000 -2.799185000 2.737033000
H -0.015663000 -2.925882000 3.713840000

Cartesian coordinate of model IM1···III for 1·(4-NC5F4)2Te (in Å)

E = – 26626.6018479

Te 2.801385000 -0.684880000 -1.000556000

F 4.367693000 2.225153000 -0.938278000
F 4.364682000 -1.724380000 1.673735000
F 6.078821000 -0.504950000 3.316845000
F 6.033755000 3.285533000 0.881586000
N 6.056762000 1.383180000 2.088790000
72
 C 4.268466000 0.191026000 0.270470000
C 4.748582000 -0.478054000 1.385048000
C 5.620644000 2.012797000 1.032580000
C 5.631713000 0.148400000 2.233396000
C 4.746587000 1.480474000 0.103219000
H 1.851557000 0.052463000 -0.283190000
Pt -2.230059000 -0.232118000 -0.363275000
O -1.251772000 0.436976000 -1.985634000
O -1.280489000 -2.088773000 -0.443742000
N -3.288970000 -0.692057000 1.258964000
C -3.958439000 -2.131925000 3.053131000
H -3.848315000 -2.928192000 3.522465000
C -3.152198000 -1.834957000 1.957953000
H -2.496593000 -2.444859000 1.703615000
C -4.223872000 0.220782000 1.647434000
C -3.244817000 1.457649000 -0.187956000
C -3.106695000 2.596176000 -0.970234000
H -2.452409000 2.632011000 -1.630437000
C -0.379776000 -0.250530000 -2.637432000
C -5.054009000 -0.019125000 2.744036000
H -5.681559000 0.614831000 3.008086000
C -4.200643000 1.439193000 0.834446000
C -5.069431000 2.543857000 1.027792000
H -5.716688000 2.521061000 1.692849000
C 0.223116000 0.461975000 -3.812775000
H -0.095289000 1.366328000 -3.837979000
H 1.180211000 0.460124000 -3.731900000
H -0.028651000 0.011812000 -4.622747000
C -3.952489000 3.688937000 -0.763788000
H -3.853737000 4.451258000 -1.287016000
C -4.943402000 3.651078000 0.214859000
H -5.518979000 4.372292000 0.322913000
C -0.435120000 -2.412721000 -1.332374000
C -4.933340000 -1.212120000 3.431575000
H -5.501838000 -1.400561000 4.144296000
C 0.029191000 -1.564395000 -2.359982000
H 0.683898000 -1.917500000 -2.918057000
C 0.110453000 -3.807074000 -1.266247000
H -0.365285000 -4.367794000 -1.882768000
H 1.043200000 -3.798169000 -1.495475000
H 0.004889000 -4.150462000 -0.375430000

Cartesian coordinate of model IM2···III for 1·(4-NC5F4)2Se (in Å)

E = – 19840.4740931

73
F -2.468711000 -2.350202000 1.910888000
F -0.474961000 2.581848000 2.387610000
F -2.931170000 2.333872000 1.326838000
F -0.033821000 -1.867331000 2.917296000
N -0.263099000 0.351238000 2.656774000
C -2.030328000 -1.097865000 1.973525000
C -0.781776000 -0.837437000 2.508079000
C -1.009095000 1.371959000 2.238955000
C -2.266441000 1.234589000 1.699384000
C -2.820023000 -0.033238000 1.581699000
H -3.828468000 -0.182525000 1.198929000
Pt 0.189194000 -0.087795000 -0.785665000
O -1.256793000 1.308706000 -1.312002000
O -1.072029000 -1.640750000 -1.099266000
N 1.575337000 1.305984000 -0.424525000
C 1.701868000 -1.284067000 -0.316205000
C 1.352238000 2.628678000 -0.454785000
H 0.467846000 2.944531000 -0.603574000
C 2.906831000 -0.624642000 -0.100485000
C 3.891853000 1.729093000 0.028131000
H 4.765370000 1.400947000 0.204408000
C 2.824780000 0.827280000 -0.161579000
C 2.378889000 3.553085000 -0.276055000
H 2.204098000 4.485112000 -0.315664000
C 4.034011000 -2.730713000 0.219059000
H 4.826358000 -3.225002000 0.386058000
C -2.281838000 -1.515061000 -1.500757000
C 1.656821000 -2.665614000 -0.218444000
H 0.832656000 -3.120284000 -0.339831000
C -2.952580000 -0.314726000 -1.777380000
H -3.860728000 -0.390709000 -2.050766000
C 4.076851000 -1.349172000 0.140795000
H 4.902753000 -0.893201000 0.248171000
C 3.665209000 3.080459000 -0.039094000
H 4.384809000 3.691574000 0.075781000
C -3.011966000 -2.807288000 -1.680281000
H -3.299475000 -2.892038000 -2.613698000

74
 H -3.798271000 -2.821774000 -1.094551000
H -2.419509000 -3.551294000 -1.451746000
C 2.814969000 -3.391049000 0.054112000
H 2.775646000 -4.337317000 0.126880000
C -2.429221000 0.989896000 -1.697214000
C -3.314798000 2.131126000 -2.086897000
H -2.866200000 2.978325000 -1.881077000
H -4.155653000 2.076702000 -1.586080000
H -3.503010000 2.085359000 -3.047996000

Cartesian coordinate of model IM2···III for 1·(4-NC5F4)2Te (in Å)

E = – 19840.3934017

F -2.135536000 -2.268177000 2.181317000

F -2.601440000 2.395487000 1.499065000
F -0.086524000 2.656729000 2.406048000
F 0.358787000 -1.785996000 3.024970000
N 0.125697000 0.434780000 2.698745000
C -2.494853000 0.045169000 1.804559000
C -0.625003000 1.442561000 2.321026000
C -1.682254000 -1.010186000 2.194209000
C -0.400902000 -0.760302000 2.628268000
C -1.927500000 1.297205000 1.858175000
H -3.521069000 -0.108088000 1.475373000
Pt 0.065338000 -0.114533000 -0.832513000
O -1.194037000 -1.666794000 -1.030903000
O -1.422251000 1.271397000 -1.304423000
N 1.466894000 1.276021000 -0.573416000
C 2.266907000 3.533197000 -0.482489000
H 2.087867000 4.446148000 -0.514403000
C 1.239319000 2.603436000 -0.614251000
H 0.367751000 2.908799000 -0.731586000
C 2.735737000 0.822980000 -0.367847000
C 1.588930000 -1.307489000 -0.418963000
C 1.550575000 -2.688964000 -0.283155000
H 0.739981000 -3.141424000 -0.343340000
C -2.440725000 -1.551657000 -1.331145000
C 3.804075000 1.710130000 -0.219784000
H 4.664590000 1.389979000 -0.068447000
75
C 2.808973000 -0.637205000 -0.276289000
C 4.009185000 -1.364253000 -0.066796000
H 4.820812000 -0.919163000 0.006754000
C -3.183541000 -2.853245000 -1.416558000
H -2.605746000 -3.570753000 -1.149582000
H -3.948388000 -2.824128000 -0.837071000
H -3.474104000 -2.995955000 -2.320705000
C 2.733018000 -3.398267000 -0.058987000
H 2.702262000 -4.323246000 0.035784000
C 3.957242000 -2.739577000 0.025565000
H 4.740245000 -3.225789000 0.145714000
C -2.617124000 0.954342000 -1.592006000
C 3.566802000 3.068911000 -0.302656000
H 4.273238000 3.671173000 -0.238382000
C -3.134045000 -0.357929000 -1.587636000
H -4.040964000 -0.442548000 -1.776255000
C -3.541588000 2.077846000 -1.954883000
H -3.603429000 2.146500000 -2.909947000
H -4.412923000 1.906154000 -1.589017000
H -3.201271000 2.900903000 -1.596290000

76
 5. Metal-involving chalcogen bonding in solutions
10 11 4 3

6 5
9 2

8 7
N 1
Pt
O O
12 16 18 20

13 15 17 19
21

14 22
Figure S26. Complex numbering scheme as key for the attribution of the NMR spectra

0.8 (4-NC5F4)2Te
Mole fraction

2·(4-NC5F4)2Te
0.6

0.4

0.2

0
Equivalents of (C5F4N)2Te

0 1 2 3 4 5 6 7 8 9 10 11
Equivalents of (4-NC5F4)2Te

-2670 -2680 -2690 -2700 -2710 -2720 -2730 -2740 -2750 -2760 -2770 -2780 -2790 -2800 -2810 -2820 -2830 -2840 -2850 -2860
f1 (ppm)

Figure S27. The 195Pt NMR titration of 2 (34 mM) with (4-NC5F4)2Te in CDCl3 at 298 K.

77
 1

0.8
Mole fraction

2
0.6 2·(4-NC5F4)2Te

0.4

0.2

0
0 1 2 3 4 5
Equivalents of 2

Equivalents of 2
450 440 430 420 410 400 390 380 370 360 350 340 330 320 310 300
f1 (ppm)

Figure S28. The 125Te NMR titration of (4-NC5F4)2Te (32 mM) with 2 in CDCl3 at 298 K.

78
Table S8. CIS Δ1H = δComplex–δComplex+СhB, ppm

H1 H2 H3 H4 H8 H9 H10 H11 H17 HtBu

2+(4-NC5F4)2Se 0.02 0 –0.01 –0.01 0.05 0.01 0 0.01 –0.01 0
2+(4-NC5F4)2Te 0.05 0.03 –0.04 0.04 0.1 0.05 –0.05 0.09 –0.08 –0.03

Table S9. CIS Δ13C = δComplex–δComplex+СhB, ppm

C1 C2 C3 C4 C5 C6 C7 C8 C9 C10 C11 C16 C18 C17 C15 C19 CtBu CtBu

2+(4-NC5F4)2Se 0.1 -0.1 -0.1 0 0.1 0.2 0 0.1 –0.1 0 0 –1 –0.1 0 0 0 0 0
2+(4-NC5F4)2Te 0 –0.3 –0.5 0 0.5 0.7 0.2 0.3 –0.2 –0.5 0.1 –1.4 –0.3 –0.5 0 –0.1 0 0

79
 H4,8 H2,9
H3 H11 H10
H1

F4D,1D

F2D,3D

Figure S29. The HOESY 19F-1H spectra of 2 + (4-NC5F4)2Te (1:1) in CDCl3 at 298 K.

Figure S30. (a) ITC blank titration curve of neat CHCl3 with (4-NC5F4)2Te in CHCl3; (b) ITC
blank curve of the titration CHCl3 with CHCl3; (c) ITC curve of the titration of 2 in CHCl3 with
(4-NC5F4)2Te in CHCl3; best fit: n = 1.0±0.1, Ka = 524±19 M–1, ΔH = –1.3±0.1 kcal/mol, ΔG = –
3.7±0.3 kcal/mol, ΔS = 8.1±0.6 cal/mol‧K at 298 K. Calculated values of the thermodynamic
80
parameters should be taken with great caution in view of the known limitations of ITC method:53
it is known54 that ITC-based calculations of Ka lead to substantially overestimated values in
cases of weak association (small Ka values; see, for example, ref. 55).

81
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