Research Article

Kazumasa Nomura* and Paul Terwilliger

Green Process Synth 2019; 8: 1–7

Self-dual Leonard pairs

Supplementary material
https://doi.org/10.1515/spma-2019-0001

Deep eutectic solvents (DESs) as powerful and

Received May 8, 2018; accepted September 22, 2018

Abstract: Let F denote a field and let V denote a vector space over F with finite positive d
recyclable catalysts
a pair A, Aand solvents
of diagonalizable F-linearfor the
maps on
∗
synthesis
V, each of which acts on an eigenbasis fo
irreducible tridiagonal fashion. Such a pair is called a Leonard pair. We consider the self
of 3,4-dihydropyrimidin-2(1H)-ones/thiones
there exists an automorphism of the endomorphism algebra of V that swaps A and A . Suc ∗

is unique, and called the duality A ↔ A∗ . In the present paper we give a comprehensiv
duality. In particular, we display an invertible F-linear map T on V such that the map X →
A ↔ A∗ . We express T as a polynomial in A and A∗ . We describe how T acts on 4 flags,
and 24 bases for V.

Keywords: Leonard pair, tridiagonal matrix, self-dual

Classification: 17B37, 15A21

1 Introduction
Let F denote a field and let V denote a vector space over F with finite positive dimen
pair A, A∗ of diagonalizable F-linear maps on V, each of which acts on an eigenbasis for
irreducible tridiagonal fashion. Such a pair is called a Leonard pair (see [13, Definition 1.1
A, A∗ is said to be self-dual whenever there exists an automorphism of the endomorphis
swaps A and A∗ . In this case such an automorphism is unique, and called the duality A
The literature contains many examples of self-dual Leonard pairs. For instance (i) the
ated with an irreducible module for the Terwilliger algebra of the hypercube (see [4, Corol
Leonard pair of Krawtchouk type (see [10, Definition 6.1]); (iii) the Leonard pair associated
module for the Terwilliger algebra of a distance-regular graph that has a spin model in th
bra (see [1, Theorem], [3, Theorems 4.1, 5.5]); (iv) an appropriately normalized totally bip
(see [11, Lemma 14.8]); (v) the Leonard pair consisting of any two of a modular Leonard t
Definition 1.4]); (vi) the Leonard pair consisting of a pair of opposite generators for the
bra, acting on an evaluation module (see [5, Proposition 9.2]). The example (i) is a specia
examples (iii), (iv) are special cases of (v).
Let A, A∗ denote a Leonard pair on V. We can determine whether A, A∗ is self-dual in
By [13, Lemma 1.3] each eigenspace of A, A∗ has dimension one. Let {θ i }di=0 denote an or
values of A. For 0 ≤ i ≤ d let v i denote a θ i -eigenvector for A. The ordering {θ i }di=0 is
whenever A∗ acts on the basis {v i }di=0 in an irreducible tridiagonal fashion. If the ordering
then the ordering {θ d−i }di=0 is also standard, and no further ordering is standard. Similar
A∗ . Let {θ i }di=0 denote a standard ordering of the eigenvalues of A. Then A, A∗ is self-dual
is a standard ordering of the eigenvalues of A∗ (see [7, Proposition 8.7]).

*Corresponding Author: Kazumasa Nomura: Tokyo Medical and Dental University, Ichikawa, 272-0827
E-mail: knomura@pop11.odn.ne.jp
Paul Terwilliger: Department of Mathematics, University of Wisconsin, Madison, WI53706, USA, E-mail:
terwilli@math.wisc.edu
Figure S1: FTIR and 1H NMR spectra of ChCl/PTSA (1:2).

Open Access. © 2019 Cui et al., published byOpen

De Gruyter.
Access. ©This work
2019 is licensed
Kazumasa under
Nomura andthe Creative
Paul Commons
Terwilliger, published by De Gruyter. This work is license
Attribution alone 4.0 License. Attribution alone 4.0 License.
2 Y. Cui et al.: Deep eutectic solvents (DESs) as powerful and recyclable catalysts and solvents

Figure S2: FTIR and 1H NMR spectra of ChCl/TCA (1:2).

 Y. Cui et al.: Deep eutectic solvents (DESs) as powerful and recyclable catalysts and solvents 3

Figure S3: FTIR and 1H NMR spectra of ChCl/MCA (1:2).

4 Y. Cui et al.: Deep eutectic solvents (DESs) as powerful and recyclable catalysts and solvents

Figure S4: FTIR and 1H NMR spectra of ChCl/PA (1:2).

 Y. Cui et al.: Deep eutectic solvents (DESs) as powerful and recyclable catalysts and solvents 5

Figure S5: FTIR and 1H NMR spectra of ChCl/EG (1:2).

6 Y. Cui et al.: Deep eutectic solvents (DESs) as powerful and recyclable catalysts and solvents
Spectral data of the products:
3a:
Melting point: 202-204°C; 1H NMR (500 MHz, DMSO-d6):
δ 1.09 (t, 3H, J = 7.0 Hz,CH3), 2.25 (s, 3H, CH3), 3.98 (q, 2H,
J = 7.0 Hz, CH2), 5.14 (s, 1H, CH), 7.23–7.33 (m, 5H, ArH),
7.73 (s, 1H, NH), 9.18 (s, 1H, NH); 13C NMR (125 MHz, DMSO-
d6): δ 14.55, 18.24, 54.43, 59.65, 99.73, 126.71, 127.73, 128.86,
145.34, 148.82, 152.59, 165.69.
3b:
Melting point: 170-172°C; 1H NMR (500 MHz, DMSO-d6):
δ 1.10 (t, 3H, J = 7.0 Hz,CH3), 2.23 (s, 3H, CH3), 2.26 (s, 3H,
CH3),3.98 (q, 2H, J = 7.0 Hz, CH2), 5.10 (s, 1H, CH), 7.10-7.13
(m, 4H, ArH), 7.67(s, 1H, NH), 9.14 (s, 1H, NH); 13C NMR (125
MHz, DMSO-d6):δ 14.57, 18.22, 21.11, 54.09, 59.62, 99.89,
126.61, 129.36, 136.83, 142.43, 148.61, 152.63, 165.83.
3c:
Melting point: 203-204°C; 1H NMR (500 MHz, DMSO-d6):
δ 1.10 (t, 3H, J = 7.0 Hz,CH3), 2.23 (s, 3H, CH3), 3.72 (s, 3H,
CH3), 3.97 (q, 2H, J = 6.8 Hz, CH2), 5.09 (s, 1H, CH), 6.88 (d,
J = 7.2 Hz, 2H, ArH), 7.14 (d, J = 8.0 Hz, 2H, ArH), 7.66 (s,
1H, NH), 9.14 (s, 1H, NH); 13C NMR (125 MHz, DMSO-d6):
δ 14.58, 18.22, 53.80, 55.54, 59.61, 100.05, 114.18, 127.86,
137.53, 148.47, 152.61, 158.92, 165.85.
3d:
Melting point: 174-176°C; 1H NMR (500 MHz, DMSO-d6): δ
1.09 (t, 3H, J = 7.0 Hz, CH3), 2.25 (s, 3H, CH3), 3.97 (q, 2H,
J = 7.0 Hz, CH2), 5.14 (s, 1H, CH), 7.15 (d, 2H, J = 8.2 Hz,ArH),
7.26 (d, 2H, J = 8.2 Hz, ArH), 7.75 (s, 1H, NH), 9.23 (s, 1H,
NH); 13C NMR (125 MHz, DMSO-d6): δ 14.54, 18.25, 53.80,
59.68, 99.58, 115.68, 128.68, 128.71, 141.65, 149.01, 152.44,
165.72.
3e:
Melting point: 214-215°C; 1H NMR (500 MHz, DMSO-d6):
δ 1.09 (t, 3H, J = 7.0 Hz, CH3), 2.27 (s, 3H, CH3), 3.98 (q, 2H,
J = 7.0 Hz, CH2), 5.14 (s, 1H, CH), 7.24 (d, J = 8.2 Hz, 2H,
ArH), 7.39 (d, J = 8.3 Hz, 2H, ArH), 7.76 (s, 1H, NH), 9.23 (s,
1H, NH); 13C NMR (125 MHz, DMSO-d6): δ 14.54, 18.27, 53.89,
59.72, 99.31, 128.66, 128.86, 132.25, 144.27, 149.19, 152.40,
165.68.
3f:
Melting point: 213-214°C; 1H NMR (500 MHz, DMSO-d6):
δ 1.08 (t, 3H, J = 7.0 Hz, CH3), 2.24 (s, 3H, CH3), 3.98 (q,
2H, J = 7.0 Hz, CH2), 5.12 (s, 1H, CH), 7.18 (d, J = 8.2 Hz, 2H,
ArH), 7.53 (d, J = 8.2 Hz, 2H, ArH), 7.78 (s, 1H, NH), 9.25 (s,
1H, NH); 13C NMR (125 MHz, DMSO-d6): δ 14.55, 18.27, 53.94,
59.74, 99.22, 120.77, 129.02, 131.80, 144.67, 149.22, 152.38,
165.67.
3g:
Melting point: 206-208°C; 1H NMR (500 MHz, DMSO-d6): δ
1.10 (t, 3H, J = 7.0 Hz,
CH3), 2.27 (s, 3H, CH3), 3.98 (q, 2H, J = 7.0 Hz, CH2), 5.27 (s,
1H, CH), 7.51 (d, J = 8.2 Hz, 2H, ArH), 7.88 (s, 1H, NH), 8.22
(d, J = 8.3 Hz, 2H, ArH), 9.34 (s, 1H, NH); 13C NMR (125 MHz,
DMSO-d6): δ 14.52, 18.34, 54.15, 59.86, 98.66, 124.31, 128.13,
147.20, 149.86, 152.21, 152.47, 165.53.
3h:
Melting point: 233-235°C; 1H NMR (500 MHz, DMSO-d6):
δ 1.10 (t, 3H, J = 7.0 Hz, CH3), 2.23 (s, 3H, CH3), 3.97 (q, 2H,
J = 6.8 Hz, CH2), 5.03 (s, 1H, CH), 6.68 (d, J = 7.2 Hz, 2H,
ArH), 7.02 (d, J =7.3 Hz, 2H, ArH), 7.63 (s, 1H, NH), 9.09
(s, 1H, OH); 9.35 (s, 1H, NH); 13C NMR (125 MHz, DMSO-
d6): 14.58, 18.21, 53.87, 59.57, 100.15, 115.43, 127.87, 135.90,
148.26, 152.63, 157.00, 165.88.
3i:
Melting point: 192-193°C; 1H NMR (500 MHz, DMSO-d6):
δ 1.03 (t, 3H, J = 7.0 Hz, CH3), 2.27 (s, 3H, CH3), 3.99 (q, 2H,
J = 7.0 Hz, CH2), 5.30 (s, 1H, CH), 7.64-7.71 (m, 2H, ArH),
7.89 (s, 1H, NH), 8.08-8.15 (m, 2H, ArH), 9.36 (s, 1H, NH);
13
C NMR (125 MHz, DMSO-d6): δ 14.49, 18.33, 54.02, 59.86,
98.80, 121.47, 122.83, 130.72, 133.46, 147.46, 148.22, 149.90,
152.24, 165.54.
3j:
Melting point: 213-215°C; 1H NMR (500 MHz, DMSO-d6): δ
0.99 (t, 3H, J = 7.0 Hz, CH3), 2.30 (s, 3H, CH3), 3.88 (q, 2H, J =
7.0 Hz, CH2), 5.53 (s, 1H, CH), 7.16-7.46 (m, 4H, ArH), 7.72 (s,
1H, NH), 9.23 (s, 1H, NH); 13C NMR (125 MHz, DMSO-d6): δ
14.37, 18.13, 51.93, 59.53, 98.34, 128.21, 129.84, 129.53, 129.81,
132.13, 142.19, 149.76, 151.78, 165.41.
3k:
Melting point: 184-186°C; 1H NMR (500 MHz, DMSO-d6): δ
1.10 (t, 3H, J = 7.0 Hz, CH3), 2.26 (s, 3H, CH3), 4.00 (q, 2H, J
= 7.0 Hz, CH2), 5.14 (s, 1H, CH), 7.22-7.48 (m, 4H, ArH), 7.80
(s, 1H, NH), 9.28 (s, 1H, NH); 13C NMR (125 MHz, DMSO-
d6): δ 14.52, 18.29, 54.06, 59.77, 99.06, 121.99, 125.74, 129.64,
130.62, 131.29, 147.96, 149.43, 152.36, 165.62.
3l:
Melting point: 225-227°C; 1H NMR (500 MHz, DMSO-d6): δ
1.10 (t, 3H, J = 7.0 Hz, CH3), 2.27 (s, 3H, CH3), 3.99 (q, 2H,
J = 7.0 Hz, CH2), 5.30 (s, 1H, CH), 7.64-7.72 (m, 2H, ArH), 7.89
(s, 1H, NH), 8.07-8.16(m, 2H, ArH),9.36 (s, 1H, NH);13C NMR
(125 MHz, DMSO-d6): δ 14.49, 18.33, 54.02, 59.86, 98.58,
121.47, 122.86, 130.72, 133.46, 147.53, 148.25, 149.96,152.43,
165.62.
3m:
Melting point: 220-222°C; 1H NMR (500 MHz, DMSO-d6): δ
1.04 (t, 3H, J = 7.0 Hz,CH3), 2.26 (s, 3H, CH3), 3.78 (s, 3H,
CH3), 3.92 (q, 2H, J = 7.0 Hz, CH2), 5.52 (s, 1H, CH), 6.60-
6.87 (m, 3H, ArH), 7.08 (s, 1H, NH), 8.74 (s, 1H, OH); 9.10 (s,
1H, NH); 13C NMR (125 MHz, DMSO-d6): δ 14.52, 18.17, 49.21,
56.32, 59.44, 98.50, 111.23, 119.00, 119.46, 130.98, 143.14,
147.97, 148.94, 152.65, 165.93.
 Y. Cui et al.: Deep eutectic solvents (DESs) as powerful and recyclable catalysts and solvents
3n:
Melting point: 208-209°C; 1H NMR (500 MHz, DMSO-d6):
δ 1.10 (t, 3H, J = 7.0 Hz,CH3), 2.29 (s, 3H, CH3), 4.01 (q, 2H,
J = 6.8 Hz, CH2), 5.18 (s, 1H, CH), 7.21–7.38 (m, 5H, ArH), 9.64
(s, 1H, NH), 10.32 (s, 1H, NH); 13C NMR (125 MHz, DMSO-
d6): δ 14.47, 17.62, 54.51, 60.01, 101.21, 126.85, 129.03, 128.86,
143.95, 145.48, 165.61, 174.72.
3o:
Melting point: 209-211°C; 1H NMR (500 MHz, DMSO-d6):
δ 2.25 (s, 3H, CH3), 3.53 (s, 3H, CH3), 5.14 (s,1H, CH), 7.22-7.34
(m, 5H, ArH), 7.76 (s, 1H, NH), 9.22 (s, 1H, NH); 13C NMR (125
MHz, DMSO-d6): δ 18.30, 51.26, 54.26, 99.46, 126.64, 127.76,
128.93, 145.15, 149.18, 152.63, 166.31.
3p:
Melting point: 192-194°C; 1H NMR (500 MHz, DMSO-d6):
δ 2.24 (s, 3H, CH3), 3.52 (s, 3H, CH3), 3.72 (s, 3H, CH3), 5.09
(s, 1H, CH), 6.87 (d, 2H, J = 8.5 Hz,ArH), 7.14 (d, 2H, J = 8.3
Hz, ArH), 7.70 (s, 1H, NH), 9.20 (s, 1H, NH); 13C NMR (125
MHz, DMSO-d6): δ 18.28, 51.24, 53.63, 55.52, 99.72, 114.23,
127.80, 137.32, 148.83, 152.63, 158.92, 166.33.
3q:
Melting point: 245-249°C; 1H NMR (500 MHz, DMSO-d6):
δ 2.27 (s, 3H, CH3), 3.54 (s, 3H, CH3), 5.28 (s, 1H, CH), 7.51
(d, 2H, J = 8.4 Hz, ArH), 7.93 (s, 1H, NH), 8.22 (d, 2H, J = 8.2
Hz, ArH), 9.40 (s, 1H, NH); 13C NMR (125 MHz, DMSO-d6):
δ 18.40, 51.40, 53.99, 98.43, 124.36, 128.06, 147.20, 150.12,
152.27, 166.04.
3r:
Melting point: 235-237°C; 1H NMR (500 MHz, DMSO-d6):
δ 2.25 (s, 3H, CH3), 3.53 (s, 3H, CH3), 5.12 (s, 1H, CH), 7.18
7
(d, 2H, J = 8.1 Hz, ArH), 7.53 (d, 2H, J = 8.2 Hz, ArH), 7.81
(s, 1H, NH), 9.29 (s, 1H, NH); 13C NMR (125 MHz, DMSO-d6):
δ 18.33, 51.33, 53.77, 98.96, 120.84, 128.96, 131.86, 144.48,
149.52, 152.42, 166.17.
3s:
Melting point: 225-226°C; 1H NMR (500 MHz, DMSO-d6):
δ 2.29 (s, 3H, CH3), 3.53 (s, 3H, CH3), 5.18 (s, 1H, CH), 7.20-
7.38 (m, 5H, ArH), 9.69 (s, 1H, NH), 10.37 (s, 1H, NH); 13C
NMR (125 MHz, DMSO-d6): δ 17.68, 51.59, 54.34, 100.88,
126.78, 128.19, 129.11, 143.76, 145.81, 166.11, 174.73.
3t:
Melting point: 233-234°C; 1H NMR (500 MHz, DMSO-d6):
δ 2.11 (s, 3H, CH3), 2.29 (s, 3H, CH3), 5.26 (s, 1H, CH), 7.24-
7.34 (m, 5H, ArH), 7.83 (s, 1H, NH), 9.19 (s, 1H, NH); 13C NMR
(125 MHz, DMSO-d6): δ 19.38, 30.79, 54.27, 110.04, 126.99,
127.79, 128.99, 144.71, 148.58, 152.68, 194.70.
3u:
Melting point: 254-256°C; 1H NMR (500 MHz, DMSO-d6):
δ 2.19 (s, 3H, CH3), 2.32 (s, 3H, CH3), 5.39 (d, J = 4.0 Hz, 1H,
CH), 7.51 (d, J = 8.5 Hz, 2H, ArH), 7.99 (s, 1H, NH), 8.21 (d,
J = 8.5 Hz, 2H, ArH), 9.36 (s, 1H, NH); 13C NMR (125 MHz,
DMSO-d6): δ 19.59, 31.11, 53.62, 109.92, 124.29, 128.14, 147.15,
149.54, 152.03, 152.44, 194.38.
3v:
Melting point: 158-159˚C; 1H NMR (500 MHz, DMSO-d6):
δ 0.71 (t, J = 7.0 Hz, 3H, CH3), 3.70 (q, J = 7.0 Hz, 2H, CH2),
5.24 (s, 1H, CH), 7.27-7.41 (m, 10H, ArH), 7.86 (s, 1H, NH),
9.30 (s, 1H, NH); 13C NMR (125 MHz, DMSO-d6): δ 13.85,
54.63, 59.55, 100.88, 126.78, 127.89, 128.19, 128.81, 129.00,
129.34, 135.55, 144.88, 149.43, 152.59, 165.58.