i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6

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Hydrogen production with a designed

clathrochelate-based electrocatalytic materials:
Synthesis, X-ray structure and redox-properties of
the iron cage complexes with pendant (poly)
aryl-terminated ribbed substituents

Oleg A. Varzatskii a, Dmitriy A. Oranskiy b, Serhii V. Vakarov a,

Nina V. Chornenka a, Alexander S. Belov c, Anna V. Vologzhanina c,
Alexander A. Pavlov c, Sergey A. Grigoriev d,*, Artem S. Pushkarev d,e,
Pierre Millet f, Valery N. Kalinichenko c, Yan Z. Voloshin c,g,
Alexey G. Dedov g
a
Vernadskii Institute of General and Inorganic Chemistry NASU, 03080 Kiev, Ukraine
b
PBMR Labs Ukraine, 02094 Kiev, Ukraine
c
Nesmeyanov Institute of Organoelement Compounds of the Russian Academy of Sciences, 119991 Moscow, Russia
d
National Research University “Moscow Power Engineering Institute”, 111250 Moscow, Russia
e
National Research Centre “Kurchatov Institute”, 123182 Moscow, Russia
f
Institut de Chimie Mol
eculaire et des Mat
eriaux d’Orsay, Universit
e Paris-Sud 11, 91405 Orsay, France
g
Gubkin Russian State University of Oil and Gas, 119991 Moscow, Russia

article info abstract

Article history: Cage iron(II) complexes with one, two or six terminal (poly)aromatic group(s), designed for
Received 23 February 2017 effective physical adsorption on the carbonaceous substrates, were prepared by nucleo-
Received in revised form philic substitution of their mono-, di- and hexachloroclathrochelate precursors with 3-
2 May 2017 arene-1(9)-yl-propane-1 thiolate anions. Their cyclic voltammograms contain the single
Accepted 12 May 2017 Fe2þ/þ reduction wave in the cathodic potential range and two oxidation waves in the anodic
Available online xxx potential range, assigned to a metal-centered Fe2þ/3þ process and to oxidation of their
arylalkylsulfide groups, respectively. Iron(II) hexaphenanthrenylsulfide clathrochelate with
Keywords: six terminal polyaromatic groups was either immobilized or impregnated on the cathode of
Hydrogen production gas diffusion electrode and its electrochemical activity with regard to hydrogen evolution
Hydrogen evolution reaction reaction (HER) was tested in a proton exchange membrane water electrolysis cell for
Water electrolysis hydrogen production. It was shown that effective immobilization of this (pre)catalyst on the
Proton exchange membrane surface of appropriate carbonaceous electrode materials can be successfully used for
Clathrochelate improving an efficiency of clathrochelate-based hydrogen-producing systems.
Electrocatalysis © 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
E-mail address: sergey.grigoriev@outlook.com (S.A. Grigoriev).
http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
0360-3199/© 2017 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6
Introduction
Molecular hydrogen, if obtained from an appropriate source, is a
potential alternative to carboniferous fossil fuels [1]. During the
last decades, the electrocatalytic process for the reduction of Hþ
ions to molecular hydrogen with 3d-transition metal complexes
has been widely used for production of H2 as ecologically
friendly fuel [2e8]. Modern hydrogen energy is therefore heavily
focused on the search for of catalytic systems that produce
hydrogen from water. Cage 3d-metal complexes [9,10] have
been recently recognized [11e20] as prospective molecular (pre)
catalysts in various acidic media: they can be homogeneous
catalysts [11] or precursors (precatalysts) of the catalytically
active nanoparticles [14]. Indeed, a wide use of various elec-
trochemical systems (fuel cells, electrolyzers etc.) in hydrogen
energy, high technology industries, green hybrid and hydrogen-
based transports and other different fields of modern social and
economic life causes a substantial increase in consumption of
precious metals, which are currently used as electrocatalysts
for hydrogen production [21]. Their high cost significantly limits
a wide-spread use of such electrocatalytic systems in hydrogen
energy. The use of cheap and abundant non-platinum metal
compounds in fuel cells, electrolyzers and electrochemical
hydrogen compressors/concentrators [22] will make hydrogen
energy, more available than ever.
Effective immobilization of the clathrochelate (pre)catalysts
on the surface of an appropriate carbonaceous electrode mate-
rial can be used for improving both the efficiency and the dura-
bility of such hydrogen-producing systems. Rational design of
immobilized clathrochelate (pre)catalysts will allow performing
hydrogen production on the surface of modified carbonaceous
materials, graphene or its oxide. The use of apical or ribbed
substituents with terminal (poly)aromatic groups can ensure an
efficient immobilization of a clathrochelate (pre)catalyst via
strong stacking interactions with complimentary fragments on
the surface (Scheme 1), thus making them long-living highly
Scheme 1 e Immobilization of a designed clathrochelate
molecule on the carbonaceous surface.
Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
efficient heterogeneous catalytic materials for hydrogen pro-
duction from acidic aqueous solutions, including those found in
water electrolysers with solid polymeric electrolytes. For suc-
cessful solution of these problems, synthetic pathways to the
clathrochelates with terminal functionalizing group(s), which
allow for the strong physical adsorption on the surface of such
substrates, should be developed. In the present work, we aimed
to design the ribbed-functionalized clathrochelates with termi-
nal (poly)aromatic group(s) and labile spacer fragments(s),
which ensure their efficient immobilization on a carbonaceous
surface, to study their X-ray structure and redox properties, and
to test a leader macrobicyclic compound as a cathode (pre)
catalyst in the membrane-electrode assembly (MEA) of proton
exchange membrane (PEM) water electrolysis cell.
Experimental
Materials and methods
The reagents used, FeCl2$4H2O, a-benzildioxime (H2Bd),
BF3$O(C2H5)2, triethylamine, sorbents and organic solvents
were obtained commercially (SigmaeAldrich®). Mono- and
dichloroclathrochelate precursors were prepared by conden-
sation of a macrocyclic iron(II) bis-a-benzildioximate with the
corresponding a-dioxime as described elsewhere [23,24]. Their
n-butylboron-capped hexachloroclathrochelate analog was
obtained as described in Ref. [25]. The preparation of 3-(1-
phenanthryl)propane thiol and 3-(9-phenanthryl)propane
thiol is described in Ref. [26].
Analytical data (C, H, N contents) were obtained with a
Carlo Erba model 1106 microanalyzer. Iron content was eval-
uated spectrophotometrically.
MALDI-TOF mass spectra were recorded with and without
the matrix using a MALDI-TOF-MS Bruker Autoflex II (Bruker
Daltonics) mass spectrometer in reflecto-mol mode. The
ionization was induced by UV-laser with wavelength 337 nm.
The samples were applied to a nickel plate, 2,5-
dihydroxybenzoic acid was used as the matrix. The accuracy
of measurements was 0.1%.
1
H, 11B{1H} and 13C{1H} NMR spectra were recorded from
CD2Cl2 and CDCl3 solutions with a Bruker Avance 400 and
Avance 600 spectrometers. The measurements were done
using the residual signals of CD2Cl2 (1H 5.32 ppm, 13C
54.00 ppm) and CDCl3 (1H 7.26 ppm, 13C 77.16 ppm). The 11B{1H}
NMR chemical shifts were referenced to 15% solution of
BF3$O(C2H5)2 in CDCl3 as an external standard.
UVeVis spectra of the solutions in dichloromethane were
recorded in the range 230e800 nm, with a Varian Cary 50
spectrophotometer. The individual Gaussian components of
these spectra were calculated using the Fityk program [27].
IR spectra of the solid samples (KBr tablets) in the range
400e4000 cm1 were recorded with a Perkin Elmer FT-IR
Spectrum BX II spectrometer.
Synthesis
General three-stage synthetic procedure for preparation of 3-
arene-1(9)-yl-propane-1 thiols
Allylic-1(9)-arenes. A solution of the corresponding aryl bro-
mide (0.1 mmol) in dry THF (100 ml) was added dropwise to the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6 3

intensively stirring suspension of magnesium dust (0.11 mol),
activated with iodine, in dry THF (100 ml). The reaction
mixture was stirred until the complete dissolution of metallic
magnesium (approximately 2 h) and then additionally for 2 h.
The reaction mixture was cooled to 10  C and a solution of
freshly distilled allyl bromide (0.11 mmol) in THF (50 ml) was
added. The reaction mixture was stirred for 1 h at r.t., diluted
with water (500 ml) and extracted with dichloromethane. The
solvent was evaporated from this dichloromethane extract
and the oily residue was re-distilled in vacuo.
3-Arene-1(9)-yl-propane mercaptoacetates. The corresponding
allylic arene (0.05 mol) was dissolved in dry CS2 under argon,
and freshly distilled thioacetic acid (0.08 mol) and AIBN
(50 mg) were added under intensive stirring. The reaction
mixture was stirred at 50  C; the reaction course was
controlled by gas chromatography. When the reaction was
completed, CS2 and an excess of thioacetic acid were evapo-
rated at 30  C in vacuo and the oily residue was re-distilled in
vacuo.
3-Arene-1(9)-yl-propane-1 thiol. The corresponding 3-arene-1-
yl-propane mercaptoacetate (0.1 mol) was dissolved in
ethanol (30 ml) and NaOH (0.35 mol) was added. The reaction
mixture was refluxed for 1 h under argon, then cooled to r.t.
and treated with the concentrated aqueous hydrochloric acid
up to strongly acidic media. Then the reaction mixture was
evaporated to the oily residue. This residue was redistilled in
vacuo (in the case of a phenanthrene derivative, it was
recrystallized from hexaneedichloromethane 10:1 mixture).

Scheme 2 e Synthesis of the hexaaromatic-terminated iron(II) clathrochelates.

Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6

Clathrochelates. FeBd2((Ph(CH2)3S)2Gm)(BF)2. Complex N, 8.47. Calc. for C48H42N6B2F2FeO6S2: C, 58.92; H, 4.33; N,

FeBd2(Cl2Gm)(BF)2 (0.75 g, 1 mmol) was dissolved in dichloro-
methane (30 ml), and 3-(1-phenyl)propane thiol (0.5 g,
2.5 mmol) and triethylamine (0.49 ml, 2.6 mmol) were added to
the stirring solution under argon. The reaction mixture was
stirred for 6 h; the reaction course was monitored by TLC
(eluent: dichloromethane e hexane 1:1 mixture). Then the
reaction mixture was washed with 1% aqueous hydrochloric
acid, water, Na2CO3 saturated aqueous solution and with
water once again. The dichloromethane solution was filtered
through silica gel (5-mm layer), evaporated to a small volume
(approximately 5 ml) and precipitated with hexane (15 ml).
The precipitate was flash-chromatographically separated on
silica gel (eluent: dichloromethane e hexane 2:1 mixture). The
major elute was evaporated to dryness, washed with hexane
and dried in vacuo. Yield: 0.27 g (28%). Found: C, 58.78; H, 4.40;
8.59%. UVevis (CH2Cl2): lmax, nm (103, mol1l cm1) 242(38),
265(2.1), 290(2.8), 304(2.7), 351(2.0), 454(6.0), 486(26).
FeBd2((Naph(CH2)3S)2Gm)(BF)2. This clathrochelate was
synthesized like the previous one except that 3-(1-naphthyl)
propane thiol (0.52 g, 2.5 mmol) was used instead of 3-(9-
phenyl)propane thiol. Yield: 0.35 g (32%). Found: C, 62.16; H,
4.38; N, 7.58; Fe, 5.10. Calc. for C56H46N6B2F2FeO6S2: C, 62.36; H,
4.30; N, 7.79; Fe, 5.18%. UVevis (CH2Cl2): lmax, nm (103,
mol1l cm1) 259(42), 265(2.2), 274(4.8), 285(9.5), 295(7.7),
354(2.5), 385(1.7), 468(10), 487(24).
FeBd2((Phen(CH2)3S)2Gm)(BF)2. This clathrochelate was
synthesized like the previous one except that 3-(9-
phenanthryl)propane thiol (0.631 g, 2.5 mmol) was used
instead of 3-(1-naphthyl)propane thiol. Yield: 0.35 g (30%).
Found: C, 65.05; H, 4.42; N, 6.95; Fe, 4.60. Calc. for

Scheme 3 e Synthesis of the mono- and diaromatic-terminated iron(II) clathrochelates.

Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6 5

C64H50N6B2F2FeO6S: C, 65.21; H, 4.27; N, 7.13; Fe, 4.74%. UVevis silica gel (30-mm layer, eluent: dichloromethane), filtered and
(CH2Cl2): lmax, nm (103, mol1l cm1) 238(60), 247(3.4), 255(110), evaporated to dryness. The solid residue was dried in vacuo.
256(14), 271(26), 279(43), 288(30), 298(24), 300(6.9), 303(11), Yield: 0.37 g (73%). Found: C, 58.75; H, 4.00; N, 9.44; Fe, 6.35. Calc.
326(7.1), 351(0.5), 383(2.1), 472(13), 488(21). for C43H34N6B2F2FeO6S: C, 58.80; H, 3.90; N, 9.57; Fe, 6.36%. UVevis
FeBd2((Pyr(CH2)3S)2Gm)(BF)2. This clathrochelate was syn- (CH2Cl2): lmax, nm (103, mol1l cm1) 258(36), 264(1.3), 273(0.8),
thesized like the previous one except that 3-(1-pyrenyl)pro- 284(1.1), 286(4.7), 296(1.8), 353(2.6), 384(1.1), 459(9.0), 475(21).
pane thiol (0.691 g, 2.5 mmol) was used instead of 3-(9-
phenanthryl)propane thiol. Yield: 0.331 g (27%). Found: C, X-ray crystallography
66.52; H, 4.08; N, 6.82; Fe, 4.40. Calc. for C68H50N6B2F2FeO6S2:
C, 66.58; H, 4.11; N, 6.85; Fe, 4.55%. UVevis (CH2Cl2): lmax (103, Single crystals of the complexes FeBd2((Phen(CH2)3S)2Gm)(BF)2
mol1l cm1) 235(8.3), 238(107), 245(67), 259(41), 267(58), 2C6H14, FeBd2((Ph(CH2)3S)2Gm)(BF)2 1.5CH2Cl2, FeBd2((Phen-
276(73), 278(39), 288(18), 299(8.8), 314(7.4), 321(27), 329(34), (CH2)3S)2Gm) (BF)2 3CHCl3C7H16 and FeBd2((Ph(CH2)3S)2Gm)-
344(46), 346(22), 356(1.9), 377(1.0), 387(3.5), 428(1.3), 484(28).
Fe((Ph(CH2)3S)2Gm)3(Bn-C4H9)2. Complex Fe(Cl2Gm)3(Bn-
C4H9)2 (0.55 g, 0.5 mmol) was dissolved in dry dichloromethane
(30 ml), and 3-(9-phenyl)propane thiol (0.381 g, 2.5 mmol) and
triethylamine (0.417 ml, 3 mmol) were added to the stirring
solution under argon. The reaction mixture was stirred for 6 h
and then evaporated to dryness. The solid residue was dis-
solved in dry DMSO (5 ml). This solution was stirred for 6 h and
then evaporated to dryness in vacuo. The oily residue was dis-
solved in dry DMSO (5 ml) and the additional portions of 3-
phenyl-1-propane thiol (0.228 g, 1.5 mmol) and triethylamine
(0.278 ml, 2 mmol) were added. The reaction mixture was stir-
red for 3 h and then precipitated with 5% aqueous hydrochloric
acid (50 ml). The precipitate was filtered off and purified by
column chromatography on silica gel (eluent: dichloromethane
e hexane 2:1 mixture). The major elute was evaporated to
dryness, washed with hexane and dried in vacuo. Yield: 0.148 g
(22%). UVevis (hexane): lmax, nm (103, mol1l cm1) 205(81),
216(21), 228(3.8), 233(29), 273(7.4), 305(8.0), 453(4.3), 498(22).
Fe((Naph(CH2)3S)2Gm)3(Bn-C4H9)2. This clathrochelate was
synthesized like the previous one except that 3-(1-naphthyl)
propane thiol (0.81 g, 4 mmol) was used instead of 3-(9-phenyl)
propane thiol. Yield: 0.173 g (21%). Found: C, 67.06; H, 5.86; N,
5.02; Fe, 3.40. Calc. for C92H96N6B2FeO6S6: C, 66.90; H, 5.86; N,
5.09; Fe, 3.38%. UVevis (CH2Cl2): lmax, nm (103, mol1l cm1)
253(29), 266(19), 274(34), 281(14), 285(13), 291(32), 297(4.1),
303(9.0), 313(2.2), 389(0.9), 477(6.9), 502(19).
Fe((Phen(CH2)3S)2Gm)3(Bn-C4H9)2. This clathrochelate was
synthesized like the previous one except that 3-(9-phenanthryl)
propane thiol (1.008 g, 4 mmol) was used instead of 3-(1-
naphthyl)propane thiol. Yield: 0.215 g (21%). Found: C, 71.23;
H, 5.66; N, 4.13; Fe, 2.70. Calc. for C116H108N6B2FeO6S6: C, 71.38;
H, 5.58; N, 4.31; Fe, 2.86%. UVevis (CH2Cl2): lmax, nm (103,
mol1l cm1) 247(4.3), 250(122), 252(166), 257(40), 262(15),
272(19), 280(24), 284(12), 289(26), 300(40), 301(7.2), 329(7.0),
351(1.4), 385(2.3), 417(1.0), 494(19), 509(5.9).
FeBd2((Naph(CH2)3S)GmH)(BF)2 Complex FeBd2(ClGmH)(BF)2
(0.41 g, 0.58 mmol) was dissolved in dry dichloromethane (5 ml)
under argon and 3-(1-naphthyl)propane thiol (0.23 g, 1.21 mmol)
was added. Then a solution of triethylamine (0.16 ml, 1.15 mmol)
was added dropwise for 40 min; the reaction course was
controlled by TLC (eluent: dichloromethane e hexane 1:1
mixture). The reaction mixture was stirred for 2 h, then evapo-
rated to a half volume and precipitated with hexane (10 ml). The
precipitate was filtered off, washed with hexane and dried in air. Fig. 1 e General views of a clathrochelate molecule in the
Then it was washed with ethanol (20 ml, in two portions) and crystals FeBd2((Ph(CH2)3S)2Gm)(BF)2 1.5CH2Cl2 (a) and
dried in vacuo. The product was extracted with dichloromethane FeBd2((Phen(CH2)3S)2Gm)(BF)2 3CHCl3 C7H16 (b) given in
(2 ml), the extract was flash-chromatographically separated on thermal ellipsoids with p ¼ 50%.

Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
 6
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic

i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6
Table 1 e Main geometrical parameters of the iron(II) clathrochelates with terminal (poly)aromatic groups.
Parameter FeBd2((Ph(CH2)3S)2Gm)(BF)2$C6H6 FeBd2((Ph(CH2)3S)2Gm)(BF)2$1.5CH2Cl2 FeBd2((Phen(CH2)3S)2Gm)(BF)2$2C6H14 FeBd2((Phen(CH2)3S)2Gm)(BF)2$3CHCl3C7H16
FeeN (1) (
A) a
1.903 (3) a
1.908 (2) a
1.931 (4) 1.929 (4)a
FeeN(2) (
A) 1.923 (3)a 1.926 (2)a 1.916 (5)a 1.914 (4)a
FeeN (3) (
A) 1.914 (3) 1.910 (2) 1.903 (4) 1.910 (3)
FeeN (4) (
A) 1.899 (3) 1.906 (2) 1.913 (5) 1.916 (4)
FeeN (5) (
A) 1.903 (3) 1.917 (2) 1.917 (4) 1.916 (4)
FeeN (6) (
A) 1.903 (3) 1.920 (2) 1.904 (4) 1.911 (4)
BeO (
A) 1.469(6) e 1.498(5) 1.477(4) e 1.506(4) 1.476(8) e 1.499(7) 1.477(6) e 1.492(6)
av. 1.482 av. 1.486 av. 1.488 av. 1.484
NeO (
A) 1.360(4) e 1.370(4) 1.373(3) e 1.381(3) 1.361(5) e 1.372(5) 1.362(5) e 1.376(5)
av. 1.367 av. 1.376 av. 1.365 av. 1.372
C]N (
A) 1.298(5) e 1.311(5) 1.304(4) e 1.316(4) 1.304(7) e 1.325(7) 1.294(6) e 1.320(6)
av. 1.305 av. 1.310 av. 1.318 av. 1.308
CeC (
A) 1.449(6) e 1.463(5) 1.458(4) e 1.463(4) 1.442(7) e 1.465(7) 1.458(7) e 1.467(6)
av. 1.454 av. 1.460 av. 1.451 av. 1.463
BeF (
A) 1.345(5) e 1.350(5) 1.365(4) e 1.369(4) 1.341(7) e 1.360(7) 1.354(6) e 1.364(6)
av. 1.347 av. 1.367 av. 1.351 av. 1.359
N]CeC]N ( ) 9.0(4) e 12.4(4) 11.3(4) e 14.1(4) 5.2(8) e 12.6(8) 5.4(7) e 12.9(7)
av. 10.2 av. 12.5 av. 10.1 av. 10.3
( ) 24.8 24.7 25.3 25.5
a ( ) 78.2 78.4 78.6 78.4
h ( A) 2.31 2.33 2.33 2.32
a
The distance for the functionalized ribbed chelate fragment.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6 7

(BF)2 C6H6 were grown from dichloromethane e hexane, surface area, thickness of ca. 0.4 mm and porosity of 84% were
chloroform e heptane and benzene e iso-octane mixtures, used as GDE. GDE with an impregnated fine-crystalline sample
respectively, by slow evaporation at room temperature. The of the clathrochelate Fe((Phen(CH2)3S)2Gm)3(Bn-C4H9)2 (B) was
intensities of reflections were measured using a Bruker Apex II obtained using the same carbonaceous material.
CCD diffractometer with MoeKa radiation (for the crystal
FeBd2((Ph(CH2)3S)2Gm)(BF)2 C6Ha6, ¼ 0.71073  A, graphite Fabrication and testing of the membrane-electrode
monochromator) and Cu e Ka radiation (for the others assemblies
crystals, ¼ 1.54178  A, multilayer optics). The structures were
solved by the direct method and refined by full-matrix least GDEs with an immobilized and an impregnated clathrochelate
squares against F2. Non-hydrogen atoms were refined in Fe((Phen(CH2)3S)2Gm)3(Bn-C4H9)2 (A and B, respectively) were
anisotropic approximation except those for the disordered
fragments. One tris-methylene fragment of a clathrochelate
molecule in the crystal FeBd2((Ph(CH2)3S)2Gm)(BF)2 C6H6, and
carbon atoms of two chloroform solvate molecules in the
crystal FeBd2((Phen(CH2)3S)2Gm)(BF)2 3CHCl3 C7H16 are equi-
probably disordered over two sites; the corresponding carbon
atoms were refined isotropically. Unit cell of the crystal
FeBd2((Phen(CH2)3S)2Gm)(BF)2 2C6H14 contains a solvate hex-
ane molecule that has been treated as a diffuse contribution to
the overall scattering without specific atom positions by
SQUEEZE/PLATON [28]. Hydrogen atoms were included in the
refinement by the riding model with Uiso(H) ¼ nUeq(C), where
n ¼ 1.5 for methyl groups and 1.2 for the other atoms. All
calculations were made using the SHELXL-2014 [29] and OLEX2
[30] program packages. Main crystallographic data and
experimental details for all these crystals are collected in
Tables S1 (see SM). CCDC 1532514e1532517 contain the sup-
plementary crystallographic data for this paper. These data
can be obtained free of charge via http://www.ccdc.cam.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallo- Fig. 2 e Conformations of the molecule
graphic Data Centre, 12 Union Road, Cambridge CB2 1EZ, UK; FeBd2((Ph(CH2)3S)2Gm)(BF)2 in its two solvatomorphs
fax: (þ44) 1223-336-033; or e-mail: deposit@ccdc.cam.ac.uk. FeBd2((Phen(CH2)3S)2Gm)(BF)2 3CHCl3 C7H16 and
FeBd2((Phen(CH2)3S)2Gm) (BF)2 2C6H14. Red dots show the
Solution cyclic voltammetry experiments second position of a disordered tris-methylene fragment. (For
interpretation of the references to colour in this figure legend,
Cyclic voltammetry (CV) experiments were carried out in 1 mM the reader is referred to the web version of this article.)
acetonitrile solutions with 0.1 M ((n-C4H9)4N)BF4 as a supporting
electrolyte using a model Autolab Metrohm (Netherlands)
potentiostat with a conventional one-compartment three-
electrode cell (5 ml of solution) at scan rate 100 mV s1. Glassy
carbon (GC, d ¼ 3.0 mm) and Pt (d ¼ 1.6 mm) Basi electrodes were
used as working electrodes. These electrodes were thoroughly
polished and rinsed before the measurements. A platinum
counter electrode and a standard Ag/AgCl/KClaq. reference
electrode were applied; all the obtained potential values were
recalculated versus RHE. The solutions under study were thor-
oughly deaerated by passing argon through them before the CV
experiments and above them during the measurements.

Functionalization of gas diffusion electrodes with a

hexafunctionalized iron(II) clathrochelate

The complex Fe((Phen(CH2)3S)2Gm)3(Bn-C4H9)2 was immobi-

lized via a solution e dissolution cycle on the gas diffusion
electrode (GDE) of circular shape. This GDE was immersed in a
dichloromethane solution of the above clathrochelate for 3 min
followed by decantation of this solution, washing of the ob- Fig. 3 e Conformations of the molecule
tained clathrochelate-modified GDE (A) with dichloromethane FeBd2((Phen(CH2)3S)2Gm)(BF)2 in its two solvatomorphs
and its drying in air. Sheets of Sigracet® 10BB carbon paper with FeBd2((Phen(CH2)3S)2Gm)(BF)2 2C6H14 and
microporous sublayer (SGL CARBON GmbH, Germany) of 7-cm2 FeBd2((Phen(CH2)3S)2Gm)(BF)2 3CHCl3 C7H16.

Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6

studied as the cathodes of membrane-electrode assemblies supported platinum electrocatalyst [31e34] at the cathode
(MEAs) in PEM water electrolysis cell. Nafion® 117 membrane was prepared and used as a reference to compare the per-
(DuPont, USA) was used as a solid polymer electrolyte in the formance levels. Pt nanoparticles (Pt loading of approximately
above MEAs. A MEA containing the conventional carbon- 40 wt.%) were deposited onto Vulcan XC-72 using magnetron-

Fig. 4 e Supramolecular interactions of the functionalized disulfide chelate fragments of the corresponding macrobicyclic
molecules in the crystals FeBd2((Ph(CH2)3S)2Gm)(BF)2 1.5CH2Cl2 (a) and FeBd2((Phen(CH2)3S)2Gm)(BF)2 3CHCl3 C7H16 (b and c).
Hydrogen atoms, which are involved in hydrogen bonding, are depicted.

Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6
ion sputtering method [35]. Ir black, obtained by chemical
reduction of the solvato-complex H2IrCl6$6H2O with NaBH4 as
a reductant [31,32], was used as an anode electrocatalyst for
oxygen evolution reaction (OER) in all these MEAs. Both anodic
and cathodic catalytic layers were prepared by spraying Ir and
XC-72-supported Pt catalyst over the surface of the GDEs. The
catalyst and 5 wt.% Nafion® solution (Du Pont) were homog-
enized in iso-propanol using the ultrasonic bath with a
working frequency of 22e25 kHz for 20 min. The ionomer
content of the mixture on a dry basis was 5 wt.% for Ir black
and 15 wt.% for Pt/Vulcan XC-72. The resulting catalytic ink
was sprayed onto GDEs with intermittent dryings of the
deposited layers. Ir and Pt/Vulcan XC-72 catalysts loadings
were 2 and 1 mg/cm2, respectively. Porous titanium disks (7-
cm2 surface area, 0.9-mm thickness and 30%-porosity) were
used as the anodic GDEs. Sigracet® 10BB carbon paper was
applied as a GDE in case of Pt/Vulcan XC-72 as well as that in
the case of the clathrochelate Fe((Phen(CH2)3S)2Gm)3(Bn-
C4H9)2. After preparation, the MEAs were fixed in a lab-made
titanium electrolysis cell consisting of two thermostatic
half-cell with the MEA clamped in between [35]. Before their
testing, all MEAs were hot-pressed directly in the cell at 80 С
for 1 h. Currentevoltage curves were recorded at 80 С, atmo-
spheric pressure of gases and anodic water supply.
Results and discussion
Synthesis
Radical addition of thioacetic acid to allylic arenes is reported
[26] to be a key stage of the synthesis of 3-arene-1(9)-yl-pro-
pane-1 thiols. Their preparation was performed by Scheme 2
using three-step synthetic procedures that included: (i) the
synthesis of the corresponding allylic arene using a Grignard
derivative of the patent aryl bromide; (ii) the radical addition
of thioacetic acid to this allylic arene allowing to obtain the
corresponding arylpropane mercaptoacetate, and (iii) its
cleavage (deprotection) in strongly basic medium leading to a
thiolate anion followed by its protonation in acidic medium to
give the target thiol-terminated arylpropane.
Cage iron(II) complexes with one, two or six terminal (poly)
aromatic group(s) were easily prepared by Schemes 2 and 3 in
the yields from a low to a moderate under mild reaction
conditions (in dichloromethane as a solvent at room temper-
ature with the corresponding thiolate anion as a nucleophilic
agent generated in situ with triethylamine as organic base)
using nucleophilic substitution of their mono-, di- and hexa-
chloroclathrochelate precursors, respectively.
The complexes obtained were characterized using
elemental analysis, MALDI-TOF mass spectrometry, IR,
UVeVis, 1H and 13C NMR spectroscopies {see Supplementary
Materials (SM)}, and by single crystal X-ray diffraction.
X-ray structures
For each of the two clathrochelates FeBd2((Ph(CH2)3S)2Gm)-
(BF)2 and FeBd2((Phen(CH2)3S)2Gm)(BF)2, the crystals of two
their solvatomorphs {(FeBd2((Ph(CH2)3S)2Gm)(BF)2 C6H6, FeBd2-
((Ph(CH2)3S)2Gm)(BF)2 1.5CH2Cl2 and FeBd2((Phen(CH2)3S)2Gm)
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materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
9
(BF)2 2C6H14, FeBd2((Phen(CH2)3S)2Gm) (BF)2 3CHCl3 C7H16,
respectively) were studied by single crystal X-ray diffraction
method. Their molecular structures are shown in Fig. 1; main
geometrical parameters of the cage frameworks in all the X-
rayed solvatomorphs are listed in Table 1. FeeN distances in
their FeN6-coordination polyhedra vary from 1.899(3) to
1.931(4) 
A and the encapsulated iron(II) ion is situated almost
in the centres of these polyhedra, the geometry of which is
intermediate between a trigonal prism (TP, the distortion
angle 4 ¼ 0 ) and a trigonal antiprism (TAP, 4 ¼ 60 ) with 4
angeles from 24.7 to 25.5 . These values are characteristic of
the monoribbed-functionalized disulfide bis-a-benzildiox-
imate iron(II) clathrochelates [20,35,36]. Main bond lengths
and angles in their quasiaromatic polyazomethine frame-
works are also characteristic of the fluoroboron-capped cla-
throchelate iron(II) tris-dioximates [9,10,37]. The rigidity of
chelate N]CeC]N fragments causes the chelate (bite)
NeFeeN angles and the heights h of the FeN6-coordination
polyhedra persist, being in the ranges 78.2e78.6 and
2.31e2.33  A, respectively. Although the geometry of these
clathrochelate molecules are very similar in all these crystals,
the conformations of their functionalizing ribbed substituents
are affected by solvent molecules even in the X-rayed iso-
structural crystals FeBd2((Phen(CH2)3S)2Gm)(BF)2 2C6H14 and
FeBd2((Phen(CH2)3S)2Gm)(BF)2 3CHCl3 C7H16. Comparisons of
the general views of the clathrochelate molecules
FeBd2((Ph(CH2)3S)2Gm)(BF)2 and FeBd2((Phen(CH2)3S)2Gm)(BF)2
in their different solvatomorphic crystals are shown in Figs. 2
and 3. As can be seen from these Figures, main differences are
observed in the conformations of their flexible functionalizing
sulfide substituents, although the mutual orientations of
phenyl groups in a-benzildioximate chelate fragments are
only slightly different in these solvatomorphs. The lability of
the above functionalizing substituents can be explained by
absence of the strong intra- and intermolecular bonds in these
molecular crystals: all the ribbed substituents are involved
Fig. 5 e CVs for 1 mM acetonitrile solution of the
dichloroclathrochelate precursor FeBd2(Cl2Gm)(BF)2
measured with GC (in blue) and Pt (in red) electrodes at
scan rate 100 mV s¡1. (For interpretation of the references
to colour in this figure legend, the reader is referred to the
web version of this article.)
10 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6

Fig. 6 e CVs for 1 mM acetonitrile solutions of the dichloroclathrochelate precursor FeBd2(Cl2Gm)(BF)2 (in blue) and its
derivatives FeBd2((Ph(CH2)3S)2Gm)(BF)2 (in red) and FeBd2((Naph(CH2)3S)2Gm)(BF)2 (in green) measured with GC (a) and Pt (b)
electrodes at scan rate 100 mV s¡1. (For interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.)

Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6 11

only in the weak CeH/Cl, CeH … p and CeH/HeC contacts
(Fig. 4); surprisingly the stacking interactions were not
observed neither for the (CH2)3Ph fragments, nor even for the
(CH2)3Phen moieties.
Spectra
MALDI-TOF mass spectra of the cage complexes obtained (see
SM) contain in their positive ranges the intensive peaks of the
corresponding molecular ions [M]þ.
The number and position of the signals in the solution 1H,
13 1
C{ H} and 11B{1H} NMR spectra of the complexes under study
(see SM) as well as the ratios of the integral intensities of
protons in the 1H NMR spectra confirmed their composition
and symmetry. In the 13C{1H} NMR spectrum of the
monofunctionalized cage complex FeBd2((Naph(CH2)3S)
GmH)(BF)2, the signals of four types of azomethine carbon
atoms are observed, thus indicating an absence of the sym-
metry plane passing through the middles of the chelate CeC
bonds in its a-dioximate chelate fragments and through the
encapsulated iron(II) ion as well.
The solution UVevis spectra of these (poly)aromatic
terminated iron(II) clathrochelates with one, two and six
spacer ribbed sulfide substituents contain in their visible
ranges a very intensive (ε~2e3$104 mol l cm1) single asym-
metric band, deconvolution of which on its Gaussian compo-
nents gave one less and one more intensive components in
the range 410e510 nm assigned to the metal-to-ligand charge
transfer (MLCT) Fed / Lp* bands. Maxima of the above
asymmetric bands are substantially longwave-shifted as

Fig. 7 e CVs for 1 mM acetonitrile solutions of the dichloroclathrochelate precursor FeBd2(Cl2Gm)(BF)2 (in blue) and its
derivatives FeBd2((Phen(CH2)3S)2Gm)(BF)2 (in red) and FeBd2((Pyr(CH2)3S)2Gm)(BF)2 (in green) measured with GC (a) and Pt (b)
electrodes at scan rate 100 mV s¡1. (For interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.)

Fig. 8 e CVs for 1 mM dichloromethane solutions of the hexachloroclathrochelate precursor Fe(Cl2Gm)3(Bn-C4H9)2 (in blue)
and its derivative Fe((Ph(CH2)3S)2Gm)3(Bn-C4H9)2 (in red) measured with GC (a) and Pt (b) electrodes at scan rate 100 mV s¡1.
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
12 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6

compared with those of their halogenoclathrochelate pre-
cursors and the magnitudes of these shifts increase with the
number of the functionalizing sulfide ribbed substituents at a
cage framework. UV ranges of these spectra contain a series of
the intensive bands assigned to pep* transitions in a qua-
siaromatic polyazomethine cage framework as well as those
of the same nature in the terminal aromatic group(s) of the
macrobicyclic molecules under study.
Cyclic voltammetry
Cyclic voltammograms (CVs) of the dichloroclathrochelate
precursor FeBd2(Cl2Gm)(BF)2 and its macrobicyclic derivatives
were recorded for their solutions in acetonitrile at a relatively
high scan rate (100 mV s1), this scan rate has been typically
used for CV studies of analogous iron and cobalt cla-
throchelates [12,17,38,39,40]. CV of the dichloroclathrochelate
precursor FeBd2(Cl2Gm)(BF)2 measured with a glassy carbon
(GC) electrode (Fig. 5) contains one cathodic reduction and one
anodic oxidation waves assigned to the metal-centered Fe2þ/þ
and Fe2þ/3þ redox processes, respectively. The potential peak
differences E ¼ Ec e Ea, a measure of the reversibility of these
charge transfer processes, are equal to 88 and 80 mV,
respectively. Since the reference value for fully reversible one-
electron processes is equal to 56 mV [41], the heterogeneous
electron transfer processes measured for this dichlorocla-
throchelate precursor were qualified as quasireversible
ones. CVs of its monoribbed-functionalized derivatives
FeBd2((Ph(CH2)3S)2Gm)(BF)2, FeBd2((Naph(CH2)3S)2Gm)(BF)2,
FeBd2((Phen(CH2)3S)2Gm)(BF)2 and FeBd2((Pyr(CH2)3S)2Gm)(BF)2
were also recorded on a GC electrode (Figs. 6 and 7, a). The
potentials of both their reduction Fe2þ/þ and the oxidation
Fe2þ/3þ waves are shifted in the cathodic (more negative) po-
tential range by approximately 200 mV.

Fig. 9 e CVs for 1 mM dichloromethane solutions of the hexachloroclathrochelate precursor Fe(Cl2Gm)3(Bn-C4H9)2 (in blue)
and its derivatives Fe((Naph(CH2)3S)2Gm)3(Bn-C4H9)2 (in red) and Fe((Phen(CH2)3S)2Gm)3(Bn-C4H9)2 (in green) measured with
GC (a) and Pt (b) electrodes at scan rate 100 mV s¡1. (For interpretation of the references to colour in this figure legend, the
reader is referred to the web version of this article.)

Fig. 10 e CVs for 1 mM dichloromethane solutions of the monochloroclathrochelate precursor FeBd2(ClGmH)(BF)2 (in blue)
and its derivative FeBd2((Naph(CH2)3S)GmH)(BF)2 (in red) measured with GC (a) and Pt (b) electrodes at scan rate 100 mV s¡1.
(For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)

Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6 13

CV of the above dichloroclathrochelate precursor was also

Table 2 e Main characteristics of electrochemical redox processes for the iron(II) clathrochelates with terminal (poly)aromatic group(s) recorded with GC and Pt electrodes

0.078
0.256
0.076
0.297
0.080
0.593
0.095
0.198
0.193
0.781
0.109

0.093

0.152
EV
recorded for comparison on a Pt working electrode at scan rate
100 mV s1 (Fig. 5). It also contains one reduction Fe2þ/þ and
one oxidation Fe2þ/3þ waves, but on platinum the first wave

0.76
0.88
0.80
0.73
0.74
0.78
0.77
0.82
0.77
0.96
0.99

0.90

0.97
ic/ia
(Fe2þ/þ) is strongly irreversible (E ¼ 263 mV), while the second
wave (Fe2þ/3þ) remains quasireversible (E ¼ 80 mV). As

ia ∙105 A
observed on Pt (Figs. 6 and 7, b), the Fe2þ/þ reduction potentials

2.200
0.489
1.432
0.486
2.089
0.463
1.626
0.509
2.137
0.742
1.670

1.242

2.045
Cathodic reduction
for the disulfide clathrochelates FeBd2((Ph(CH2)3S)2Gm)(BF)2,
FeBd2((Naph(CH2)3S)2Gm)(BF)2, FeBd2((Phen(CH2)3S)2Gm)(BF)2
and FeBd2((Pyr(CH2)3S)2Gm)(BF)2 are shifted to the cathodic

eЕа V
potential range by approximately 200e300 and 130 mV,

0.510
0.437
0.507
0.398
0.510
0.249
0.495
0.442
1.157
0.874
1.192

1.172

1.030
respectively. At the same time, their Fe2þ/3þ oxidation poten-
tials are shifted to more negative (cathodic) ranges by
approximately 200 and 370 mV, respectively, as compared

eic ∙10 A
5

1.680
0.430
1.150
0.353
1.552
0.363
1.252
0.413
1.659
0.720
1.659
0.609
1.122
0.326
1.985
0.482
with their clathrochelate precursor FeBd2(Cl2Gm)(BF)2.
CVs of the hexasulfide iron(II) clathrochelates
Fe((Ph(CH2)3S)2Gm)3(Bn-C4H9)2, Fe((Naph(CH2)3S)2Gm)3(Bn-
C4H9)2 and Fe((Phen(CH2)3S)2Gm)3(Bn-C4H9)2 were recorded on

eЕс V
0.588
0.693
0.583
0.695
0.590
0.842
0.590
0.640
1.350
1.655
1.301
1.765
1.265
1.658
1.182
1.660
a GC working electrode (Figs. 8 and 9, a). In the cathodic po-
tential range, they also contain the single and quasireversible
reduction Fe2þ/þ wave for which DE is in the range

ia2 ∙10 A
90e190 mV at the same scan rate; its value is affected by the

10.910

13.080
5

4.628
1.807
3.016
0.988

2.327
5.937
3.050
8.685
2.809

5.303
1.970
0.818
nature of the terminal aromatic groups. The most interesting
result that was observed in the case of CVs recorded on a Pt
working electrode (Figs. 8 and 9, b) is inhibition of the reverse
re-oxidation waves. This result may be explained by steric Ea2 V

1.374
1.389
1.389
1.399
1.299
1.330
2.089
2.075
1.589
1.550
1.691
1.567
1.501
1.659
considerations: an encapsulated redox-active metallocenter is
additionally isolated from the surfaces of the working elec-
trodes by six bulky terminal aromatic groups that form strong
0.078
0.074
0.120
0.107
EV

stacking interactions with a GC surface as well as strong Pt/S

thiophilic interactions of the inherent sulfur atoms of the
Anodic oxidation

0.835

ribbed functionalizing substituents with a Pt working elec-

ia/ic
0.70
0.85
0.80

trode. These steric constraints are supposed to decrease the

rate of backward re-oxidation processes. Indeed, the above
ic·10 A

CVs contain one or two oxidation waves in their anodic po-

2.669
0.605
2.579
0.694
5

tential ranges. The first one was assigned to a metal-centered

Fe2þ/3þ process (in the potential range 0.9e1.0 V), and the
second one (in the potential range 1.5e2.0 V) to an oxidation of
1.069
1.076
1.067
1.067
Ес V

the inherent alkylsulfide ribbed fragments. The waves of

backward re-reduction Fe3þ/2þ processes were not observed
for two iron(II) clathrochelates with more bulky terminal ar-
ia$10 A
1.880
0.512
2.066
0.579
2.867
0.873
2.550
0.686
2.175
0.843
1.661
0.647
1.023
0.375
1.897
0.515
5

omatic groups, thus indicating an irreversible character of

their Fe2þ/3þ oxidation.
CV of the monofunctionalized cage complex FeBd2((-
Naph(CH2)3S)GmH)(BF)2 contains the single Fe2þ/þ reduction
1.147
1.150
1.172
1.174
1.172
1.167
0.987
0.990
0.964
0.927
0.971
0.971
0.998
0.968
1.281
1.262
Еа V

wave in the cathodic potential range. This wave measured on

EM means “electrode material” (GC or Pt).

GC (Fig. 10, a) is a quasireversible (DE is approximately 100 mV)

EMa

Gc

Gc

Gc

Gc

Gc

Gc

Gc

Gc

and is an irreversible on Pt (Fig. 10, b). Two oxidation waves,

Pt

Pt

Pt

Pt

Pt

Pt

Pt

Pt

which were observed in the anodic potential range and

assigned as discussed above, are irreversible whatever the
Fe((Naph(CH2)3S)2Gm)3(Bn-C4H9)2

Fe((Phen(CH2)3S)2Gm)3(Bn-C4H9)2

FeBd2((Naph(CH2)3S)GmH)(BF)2

working electrode.
Fe((Ph(CH2)3S)2Gm)3(Bn-C4H9)2
FeBd2((Naph(CH2)3S)2Gm)(BF)2

FeBd2((Phen(CH2)3S)2Gm)(BF)2
at scan rate 100 mV s¡1.

FeBd2((Pyr(CH2)3S)2Gm)(BF)2

We also compared CVs of the mono- and hexasulfide

FeBd2((Ph(CH2)3S)2Gm)(BF)2

clathrochelates with those of their mono- and hexa-

chloroclathrochelate precursors FeBd2(ClGmH)(BF)2 and
Fe(Cl2Gm)2(Bn-C4H9)2 (Figs. 8e10, Table 2). When a GC work-
ing electrode was used, the reduction Fe2þ/þ potentials
Complex

for hexasulfide complexes Fe((Ph(CH2)3S)2Gm)3(Bn-C4H9)2,

Fe((Naph(CH2)3S)2Gm)3(Bn-C4H9)2 and Fe((Phen(CH2)3S)2Gm)3
(Bn-C4H9)2, as well as that for their monosulfide analog FeBd2
a

((Naph(CH2)3S)GmH)(BF)2, are shifted to the cathodic (more

Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
14 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6

Fig. 11 e Currentevoltage performances of the MEAs with the clathrochelate Fe((Phen(CH2)3S)2Gm)3(Bn-С4H9)2-modified

cathodes (A and B) and that with Pt/Vulcan XC-72 (С).

negative) potential range by approximately 870e980 and 10 mV,
respectively. At the same time, the Fe2þ/3þ oxidation waves are
shifted in the same range by approximately 670e700 and
140 mV, respectively, as compared with their chlorocla-
throchelate precursors. When a Pt working electrode was used,
the corresponding potential shifts are in the range 700e810 and
of 130 mV in the cathodic part of CVs, and in the range 670e710
and of 170 mV, respectively, in their anodic part. So, an addi-
tivity of the relative effects of the substitution of one chlorine
atom by sulfide ribbed substituent on the redox potentials of the
above metal-centered processes is observed for all the cla-
throchelate systems under study.
Electrocatalytic activity with regard to HER
For practical application in electrochemical cells (our interest
in this study was for HER in acidic media), the complexes with
adequate electrochemical activity must be immobilized on the
surface of an appropriate electronic carrier. In an ideal case, a
densely packed monolayer of this complex adsorbed on the
surface of carbonaceous supporting materials of large surface
area (e.g. a powder or a foam) would form the most effective
modified electrode for HER. Carbon substrates are usually
preferred to any other supporting materials because of their
chemical inertness in the electrolyte of interest and suffi-
ciently high electronic conductivity. The iron(II) cla-
throchelate Fe((Phen(CH2)3S)2Gm)3(Bn-С4H9)2 contains six
terminal phenanthrenyl groups that favor its strong physical
adsorption on the surface of carbon substrates. This (pre)
catalyst was either immobilized by physical adsorption (A) or
impregnated using its fine-crystalline sample (B) on the
cathode of GDE. The electrochemical activity of this cage
complex with regard to HER was tested in a PEM water
electrolysis cell for hydrogen production. The experimental
currentevoltage curves shown in Fig. 11, can be modeled
using the following equation:
U ¼ Eo þ Ea þ Ec þ iRm ;
where Eo is the standard water splitting voltage; Ea and Ec are
the anodic and cathodic overvoltages, respectively; and iRm
represent the ohmic drop across the cell, which is mainly due
to the ionic resistance of the polymer membrane [31].
Cathodic overvoltage Ec was empirically confirmed at low
currents using a well-known Tafel relation:
Ec ¼ a þ b log i;
where a is the constant depending on the structural pecu-
liarities at the electrocatalyst surface; b is the Tafel slope; i is
the current density.
As can be seen from Fig. 11, the slopes of three cur-
rentevoltage curves at high current densities are the same,
indicating that the internal cell resistance (due to the ionic
resistance of the membrane) is mostly the same. However, the
currentevoltage curves measured on the MEAs with cathodes
A and B are shifted upwards to higher cell voltage values
compared to the reference Pt/Vulcan-containing cathode as
HER electrocatalyst. This is attributed to a larger HER over-
voltage on cathodes containing the above clathrochelate
complex. In addition, a difference between the curves for A
and B is observed. In the low current density domain
(approximately 0.25 A cm2) where the ohmic drop due to a
cell resistance is small, the logarithmic shape of the current e
voltage relationship is characteristic of a charge-transfer
controlled process. Curves for MEAs containing the cla-
throchelate Fe((Phen(CH2)3S)2Gm)3(Bn-С4H9)2 (A and B) are

Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 7 ) 1 e1 6
higher by approximately 200e300 mV than the reference
curve (C) obtained with Pt as a hydrogen-evolving catalyst.
This indicates that the HER overvoltage on the cathode con-
taining the clathrochelate complex is higher than that for the
Pt-containing cathode. It can also be observed that the curve
for the cathode with a physically adsorbed compound
Fe((Phen(CH2)3S)2Gm)3(Bn-С4H9)2 (A) is ca. 135 mV lower than
that with the same but impregnated clathrochelate (B). This
suggests that the strong surface physical adsorption might be
better than an impregnation of such (pre)catalyst. The use of a
solution e dissolution technique might allow for the forma-
tion of the strongly physically adsorbed self-assembled
monolayers on the surface of a carbonaceous material, even
inside its pores. So, in this case, the relative surface concen-
tration of the catalytically-active metallocenters might be
higher than that of the clathrochelate-impregnated cathode
(B); even if at larger current density values, the difference
between cathodes A and B tends to decrease. In this region,
thermal effects and ohmic cell resistances tend to smooth out
differences. It is also no indication that the complex
Fe((Phen(CH2)3S)2Gm)3(Bn-С4H9)2 remains chemically stable at
low cathode potential (high current densities).
Conclusions
We elaborated the synthetic pathway for preparation and
obtained the first iron(II) clathrochelates with terminal (poly)
aromatic group(s) allowing their effective immobilization on
the surface of appropriate carbonaceous electrode materials
via the strong physical adsorption. These designed cage
compounds seem to be prospective (pre)catalysts for prepa-
ration of the efficient cathodes for hydrogen evolution in the
industrial PEM water electrolyzers.
Acknowledgments
The synthesis of cage complexes was supported by Russian
Science Foundation (grant 17-13-01468). Y.Z.V., S.A.G. and
V.N.K. also thank the Russian Foundation for Basic Research
(grants 14-29-04063 and 15-29-01112) and the Russian Acad-
emy of Sciences (program 7) for the support of electrochemical
studies. The synthesis of Pt/C and Ir catalysts was supported
by the Russian Foundation for Basic Research (grant 16-08-
01070). Fabrication and tests of MEAs were financially sup-
ported by the Ministry of Education and Science of the Russian
Federation within the framework of government task in the
field of scientific activities (project No. 16.7113.2017/6.7).
A.G.D. also thanks the Ministry of Education and Science of
the Russian Federation (basic part of the State assignment
“Scientific Research Management,” profile no. 1422) for the
financial support.
Appendix A. Supplementary data
Supplementary data related to this article can be found at
http://dx.doi.org/10.1016/j.ijhydene.2017.05.092.
Please cite this article in press as: Varzatskii OA, et al., Hydrogen production with a designed clathrochelate-based electrocatalytic
materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
15
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materials: Synthesis, X-ray structure and redox-properties of the iron cage complexes with pendant (poly)aryl-terminated ribbed
substituents, International Journal of Hydrogen Energy (2017), http://dx.doi.org/10.1016/j.ijhydene.2017.05.092
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