Ligand Coordination Site-Directed Assembly of Copper(I) Iodide

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Ligand Coordination Site-Directed Assembly of Copper(I) Iodide Complexes of ((Pyridyl)-1-pyrazolyl)pyridine Jun-Chi Li,† Hong-Xi Li,*,† Hai-Yan Li,† Wei-Jie Gong,† and Jian-Ping Lang*,†,‡ †

State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials, College of Chemistry, Chemical Engineering and Materials Science, Soochow University, Suzhou 215123, Jiangsu, People’s Republic of China ‡ State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, Shanghai 200032, People’s Republic of China S Supporting Information *

ABSTRACT: A series of ((pyridinyl)-1H-pyrazolyl)pyridine (pypzpy) ligands in which the pyrazolyl ring at 1- and 3-positions is modified by two 2-, 3-, or 4pyridyl groups were prepared. Reaction of CuI with 2-(1-(pyridin-2-yl)-1Hpyrazolyl)pyridine (2,2′-pypzpy) in MeCN at room temperature or solvothermal reaction of the same components at 120 °C afforded one binuclear complex [{(2,2′-pypzpy)Cu}(μ-I)]2 (1). Treatment of CuI with 3-(1-(pyridin-2-yl)-1Hpyrazolyl)pyridine (3,2′-pypzpy) at room temperature or at 120 °C produced one-dimensional (1D) polymer [{Cu3(μ3-I)3}(μ-3,2′-pypzpy)]n (2) and one twodimensional (2D) polymer [{Cu2(μ-I)(μ3-I)}2(3,2′-pypzpy)2]n (3), respectively. Similar reactions of CuI with 4-(1-(pyridin-2-yl)-1H-pyrazolyl)pyridine (4,2′pypzpy) at room temperature or at 150 °C yielded one 1D polymeric complex [{Cu(μ3-I)}2(4,2′-pypzpy)2{Cu(μ-I)}2]n (4). Complexes [{Cu3(μ3-I)3}(μ-2,3′pypzpy)]n (5), [(CuI)(μ-2,3′-pypzpy)]2 (6), [(Cu2I2)(3,3′-pypzpy)] (7), [(CuI)(4,3′-pypzpy)] (8), [{Cu(μ3-I)}2(μ-2,4′-pypzpy)2{Cu(μ-I)}2]n (9), [(CuI)(3,4′pypzpy)] (10), and [(CuI)(μ-4,4′-pypzpy)]n (11) could be isolated by solution reactions or solvothermal reactions of CuI with 2-, 3-, 4-(1-(pyridin-3-yl)-1H-pyrazolyl)pyridine (2,3′-, 3,3′-, 4,3′-pypzpy), or 2-, 3-, 4-(1-(pyridin-4-yl)-1H-pyrazolyl)pyridine (2,4′-, 3,4′-, 4,4′-pypzpy). Compounds 1−11 were characterized by IR, elemental analysis, powder X-ray diffraction, and singlecrystal X-ray crystallography. Complex 1 contains a normal [Cu(μ-I)]2 dimeric structure. Complexes 2 and 5 consist of a unique displaced staircase chain [Cu2(μ3-I)2]n. Complex 3 has a 2D network formed by linking chairlike [Cu2(μ-I)(μ3-I)]2 units with two pairs of 3,2′-pypzpy bridges. Complexes 4 and 9 have a rare 1D triple chain, in which one internal 1D ladder-like chain [Cu2(μ3-I)2]n is connected with two zigzag chains [Cu(μ-I)]n via 4,2′-pypzpy or 2,4′-pypzpy ligands. Compound 6 consists of two [CuI] units interconnected by two 2,3′-pypzpy ligands. Compound 11 contains a 1D chain assembled by monomeric [CuI] units and 4,4′-pypzpy ligands. The luminescence properties of 1−11 in solid state were also investigated at room temperature. These results offer an interesting insight into how the coordination sites of the pypzpy ligands do exert great impact on their coordination modes, the coordination spheres of the Cu(I) centers, the formation of the [CunIn] motifs and the topological structures of the final complexes.

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INTRODUCTION In the past decades, copper(I) complexes with nitrogen, phosphorus, and sulfur organic ligands have been extensively investigated because of their interesting structures and photochemical, photophysical properties.1−24 Copper(I) iodide complexes, in particular, demonstrate rich photophysical behavior which could be manipulated by a wide variety of cluster chromophores [CunIn]25−65 and the supporting organic ligands. With regard to N-heterocyclic organic ligands, poly(pyridyl),25−27,31−33,35,38,41 poly(triazolyl),44−46 poly(imidazolyl),47−49 pyrazine,58−60 poly(pyrazolyl),66−71 and poly(benzimidazolyl)72,73 have been extensively employed in the assembly of the [CunIn]-based coordination polymers. The nature of N-heterocyclic, the flexibility and rigidity of organic linkers, the CuI-to-ligand ratios, the reaction temperatures, and the reaction solvents play an important role in directing the © XXXX American Chemical Society

variety of [CunIn] structural formats. In addition, the coordination site of one ligand may affect the structures and properties of the resulting complexes. For example, solvothermal reactions of CuI with 1,3-bis(3-pyridylaminomethyl)benzene (3-pyamb) or 1,3-bis(2-pyridylaminomethyl)benzene (2-pyamb) at 120 °C produced one binuclear complex [{(3pyamb)Cu}(μ-I)]2 and one 2D [Cu2I2]-based polymer [(Cu2I2)(2-pyamb)]n, respectively. The similar reaction of CuI with 2-pyamb at 160 °C afforded one 2D “twisted-boat” [Cu4I4]-based polymer [(Cu4I4)(2-pyamb)2]n.27 Nevertheless, few studies have been reported to systematically investigate how a series of auxiliary ligands with the same N-heterocyclic Received: December 5, 2015 Revised: January 9, 2016

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DOI: 10.1021/acs.cgd.5b01721 Cryst. Growth Des. XXXX, XXX, XXX−XXX

Crystal Growth & Design

Article

Scheme 1. Syntheses of 2,2′-, 3,2′-, 4,2′-, 2,3′-, 3,3′-, 4,3′-, 2,4′-, 3,4′-, 4,4′-pypzpy Ligands

g, 83%). Ligands 3,2′-pypzpy and 4,2′-pypzpy were synthesized by the similar manner to that used for the synthesis of 2,2′-pypzpy. Synthesis of 2-(1-(Pyridin-3-yl)-1H-pyrazol-3-yl)pyridine (3,2′-pypzpy). A mixture containing 2-(1H-pyrazol-3-yl)pyridine (1.45 g, 10 mmol), Cs2CO3 (4.88 g, 15 mmol), 3-iodopyridine (2.26 g, 11 mmol), Cu2O (0.15 g, 1 mmol), and DMSO (20 mL) was heated at 100 °C for 24 h. After cooling to ambient temperature, the mixture was partitioned into water and dichloromethane. The brown precipitate was filtered off and the aqueous layer was extracted with CH2Cl2 (3 × 20 mL). The combined brown layers were washed with brine, dry over Na2SO4, and concentrated in vacuo. The residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate, V/V = 20:1) afforded the product as a white solid (1.88 g, 85%). Ligands 3,3′-pypzpy and 4,3′-pypzpy were prepared by the similar method to that used for 3,2′-pypzpy. Synthesis of 2-(1-(Pyridin-4-yl)-1H-pyrazol-3-yl)pyridine (2,4′-pypzpy). A mixture containing 2-(1H-pyrazol-3-yl)pyridine (1.45 g, 10 mmol), K2CO3 (2.78 g, 20 mmol) and 4-iodopyridine (2.26 g, 11 mmol) was heated at 190 °C for 24 h. After cooling to ambient temperature, the mixture was partitioned water and dichloromethane. The brown precipitate was filtered off and the aqueous layer was extracted with CH2Cl2 (3 × 20 mL). The combined brown layers were washed with brine, dried over Na2SO4, and concentrated in vacuum. The residue was purified by silica gel column chromatography (petroleum ether/ethyl acetate, V/V = 20/1) afforded the product as a white solid (1.89 g, 85%). Ligands 3,4′pypzpy and 4,4′-pypzpy were prepared by a similar approach to that used for 2,4′-pypzpy. All the nine ligands were fully characterized by melting point, 1H and 13C spectroscopy, mass spectrometry, elemental analysis, and IR (see Supporting Information). Synthesis of [(2,2′-pypzpy)Cu(μ-I)]2·MeCN (1·MeCN). Method A. To a solution containing CuI (10 mg, 0.05 mmol) in MeCN (3 mL) was added a solution of 2,2′-pypzpy (11 mg, 0.05 mmol) in MeCN (3 mL). The mixture was stirred at room temperature for 3 h and then filtered. Et2O (30 mL) was layered onto the filtrate to form yellow crystals of 1 several days later, which were collected by filtration, washed with Et2O, and dried in air. Yield: 13 mg (64% based on Cu). Anal. Calcd for C13H10CuIN4: C, 37.83; H, 2.44; N, 13.58%. Found: C, 38.13; H, 2.66; N, 13.82%. IR (KBr disk): 1603 (w), 1559 (w), 1471 (w), 1453 (w), 1433 (w), 1383 (w), 1367 (w), 1042 (w), 969 (w), 938 (w), 901 (w), 867 (w), 769 (m), 704 (w), 699 (s), 637 (m), 604 (m), 570 (m), 534 (m) cm−1. Method B. To a Pyrex glass tube (15 cm in length, 7 mm in inner diameter) was added CuI (10 mg, 0.05 mmol), 2,2′-pypzpy (11 mg, 0.05 mmol), DMF (0.5 mL), and MeCN (2 mL). The tube was sealed and heated in an oven at 120 °C for 2000 min and subsequently cooled to room temperature at a rate of 5 °C per 60 min to give a yellow solution. Et2O (10 mL) was layered onto the solution to produce yellow crystals of 1 several days later, which were collected by filtration, washed with Et2O, and dried in air. Yield: 15 mg (71% based on Cu). Synthesis of [{Cu3(μ3-I)3}(μ-3,2′-pypzpy)]n (2). Yellow crystals of 2 were prepared by a similar manner to that used for the

groups but different coordination sites to affect their coordination modes, the [CunIn] structural motifs, the coordination geometry of Cu(I) ion, the molecular architectures, and the properties of [CunIn]-based complexes. We have been interested in the syntheses, structures, and properties of [Cu n I n ]-supported coordination polymers with poly(pyrazolyl) 66−70 or poly(benzimidazolyl) 72,73 or poly(pyridyl)74 or mixed N,S-donor75,76 ligands. In this work, we synthesized a family of ((pyridinyl)-1H-pyrazolyl)pyridine (pypzpy) ligands, in which the pyrazolyl ring at 1- and 3positions is modified by two 2- or/and 3-, 4-pyridyl groups (Scheme 1). Then, we carried out the reactions of these pypzpy ligands with CuI at different temperatures and isolated 11 Cu(I)/pypzpy complexes [{(2,2′-pypzpy)Cu}(μ-I)]2 (1), [{Cu3(μ3-I)3}(μ-3,2′-pypzpy)]n (2), [{Cu2(μ-I)(μ3-I)}2(3,2′pypzpy)2]n (3), [{Cu(μ3-I)}2(4,2′-pypzpy)2{Cu(μ-I)}2]n (4), [{Cu3(μ3-I)3}(μ-2,3′-pypzpy)]n (5), [(CuI)(μ-2,3′-pypzpy)]2 (6), [(Cu2I2)(3,3′-pypzpy)] (7), [(CuI)(4,3′-pypzpy)] (8), [{Cu(μ3-I)}2(μ-2,4′-pypzpy)2{Cu(μ-I)}2]n (9), [(CuI)(3,4′pypzpy)] (10), and [(CuI)(μ-4,4′-pypzpy)]n (11). Based on the results of their single-crystal X-ray analysis, we assume that the coordination sites of these pypzpy ligands do play an important role in the formation of their different coordination modes, the different coordination sphere of the Cu(I) centers, the different [CunIn] motifs, and the different architectures of the resulting complexes. Described herein are the syntheses of these pypzpy ligands and complexes 1−11, their structural characterization, along with their luminescent properties.

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EXPERIMENTAL SECTION

General Procedure. Complexes 2-, 3-, 4-(1H-pyrazol-3-yl)pyridine were prepared according to the literature method.77−80 All other reagents were used as purchased from commercial sources without further purification. The analytical instruments for the characterization of the compounds described in this article were the same as those employed in our previous works unless otherwise noted.70 Synthesis of 2,2′-(1H-Pyrazole-1,3-diyl)dipyridine (2,2′pypzpy). A mixture containing 2-(1H-pyrazol-3-yl)pyridine (2.18 g, 15 mmol), CuI (0.29 g, 1.5 mmol), K2CO3 (2.48 g, 18 mmol), 1,10phenanthroline (0.27 g, 1.5 mmol), 2-iodopyridine (3.28 g, 16 mmol), and toluene (20 mL) was refluxed for 24 h. After cooling to ambient temperature, the mixture was partitioned between H2O and CH2Cl2. The organic layer was separated, while the aqueous layer was extracted with CH2Cl2 (3 × 20 mL). The combined organic layers were washed with brine, dried over Na2SO4, and concentrated in vacuo. The residue was purified by flash chromatography on silica gel (petroleum ether/ ethyl acetate, V/V = 20/1) to afford the product as a white solid (2.76 B



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Table 1. Crystal Data and Structure Refinement Parameters for 1·MeCN, 2−6, and 11 empirical formula formula weight crystal system space group a (Å) b (Å) c (Å) α (deg) β (deg) γ (deg) V (Å3) ρcalc (g/cm3) Z μ (mm−1) F(000) R1a wR2b GOFc

1·MeCN

2

3

4

5

6

11

C28H23Cu2I2N9 866.43 monoclinic C2/c 17.5039(8) 8.5023(3) 22.1612(12)

C13H10Cu3I3N4 793.57 triclinic P1̅ 9.4757(18) 9.7775(18) 10.737(2) 98.809(5) 108.399(4) 97.768(5) 914.7(3) 2.881 2 8.519 724 0.0676 0.1271 1.059

C13H10Cu2I2N4 603.13 monoclinic P21/n 7.5240(3) 16.8983(8) 12.2843(5)

C13H10Cu2I2N4 603.13 monoclinic P21 8.8193(3) 4.09751(18) 22.2226(8) 90.951(3)

1560.45(12) 2.567 4 34.402 1120 0.0426 0.0925 1.028

802.96(5) 2.495 2 33.428 560 0.0489 0.1236 1.038


C13H10CuIN4 412.69 orthorhombic Pbcn 8.7415(5) 14.8940(8) 10.2718(8)

92.442(4)


115.117(6) 2986.3(2) 1.927 4 3.527 1672 0.0422 0.0583 1.045

1337.35(15) 2.050 4 3.931 792 0.0314 0.0702 0.999

a R1 = Σ∥F0|−|Fc∥/Σ|F0|. bwR2 = {Σw(F02−Fc2)2/Σw(F02)2}1/2. cGOF = {Σw((F02−Fc2)2)/(n-p)}1/2, where n = number of reflections and p = total number of parameters refined.

13.58%. Found: C, 36.44; H, 2.42; N, 14.07%. IR (KBr disk): 1602 (w), 1581 (w), 1501 (w), 1487 (w), 1459 (w), 1431 (s), 1384 (s), 1338 (w), 1277 (w), 1106 (m), 1060 (m), 802 (m), 755 (m), 693 (w), 617 (w) cm−1. Synthesis of [(Cu2I2)(3,3′-pypzpy)] (7). Yellow solid 7 was prepared by a similar manner to that used for the preparation of 1 via method A, using 3,3′-pypzpy (11 mg, 0.05 mmol) and CuI (10 mg, 0.05 mmol) as starting materials. Yield: 13 mg (84% based on Cu). Anal. Calcd for C13H10Cu2I2N4: C, 25.89; H, 1.67; N, 9.29%. Found: C, 26.37; H, 1.93; N, 9.46%. IR (KBr disk): 1583 (m), 1524 (w), 1494. (s), 1483 (m), 1457 (s), 1384 (m), 1316 (w), 1275 (w), 1239 (w), 1187 (w), 1127 (m), 1053 (m), 1041 (m), 969 (w), 947 (w), 807 (w), 751 (s), 690 (m), 643 (w) cm−1. Synthesis of [(CuI)(4,3′-pypzpy)] (8). Yellow solid 8 was prepared by a similar manner to that used for the preparation of 1 via method A, using 4,3′-pypzpy (11 mg, 0.05 mmol) and CuI (10 mg, 0.05 mmol) as starting materials. Yield: 18 mg (87% based on Cu). Anal. Calcd for C13H10CuIN4: C, 37.83; H, 2.44; N, 13.58%. Found: C, 37.43; H, 2.53; N, 13.38%. IR (KBr disk): 1613 (s), 1582 (m), 1502 (s), 1487 (m), 1457 (m), 1424 (m), 1384 (s), 1368 (m), 1310 (w), 1274 (w), 1216 (w), 1127 (w), 1053 (m), 961 (w), 833 (w), 756 (m), 687 (m), 638 (m), 620 (w) cm−1. Synthesis of [{Cu(μ-I)(2,4′-pypzpy)}2{Cu(μ3-I)}2]n (9). Yellow crystals of 9 were prepared by a similar manner to that used for the preparation of 1 via method A, using 2,4′-pypzpy (11 mg, 0.05 mmol) and CuI (10 mg, 0.05 mmol) as starting materials. Yield: 13 mg (88% based on Cu). Anal. Calcd for C13H10Cu2I2N4: C, 25.89; H, 1.67; N, 9.29%. Found: C, 26.12; H, 1.70; N, 9.33%. IR (KBr disk): 1603 (s), 1574 (w), 1526 (w), 1510 (m), 1437 (m), 1383 (m), 1371 (m), 1341 (w), 1284 (w), 1219 (w), 1108 (w), 1057 (w), 1013 (w), 966 (w), 820 (m), 760 (m), 720 (m) cm−1. Synthesis of [(CuI)(3,4′-pypzpy)] (10). Yellow solid 10 was prepared by a similar manner to that used for the preparation of 1 via method A, using 3,4′-pypzpy (11 mg, 0.05 mmol) and CuI (10 mg, 0.05 mmol) as starting materials. Yield: 19 mg (91% based on Cu). Anal. Calcd for C13H10CuIN4: C, 37.83; H, 2.44; N, 13.58%. Found: C, 37.45; H, 2.66; N, 13.42%. IR (KBr disk): 1603 (s), 1571 (w), 1529 (m), 1507 (w), 1455 (w), 1427 (m), 1384 (m), 1364 (m), 1338 (w), 1310 (w), 1221 (w), 1126 (w), 1043 (w), 957 (w), 823 (w), 750 (m), 726 (w), 697 (m) cm−1. Synthesis of [(CuI)(μ-4,4′-pypzpy)]n (11). Yellow crystals of 11 were prepared in a similar manner to that used for the preparation of 1 via method B (150 °C), using 4,4′-pypzpy (11 mg, 0.05 mmol) and

preparation of 1 via method A, using 3,2′-pypzpy (11 mg, 0.05 mmol) and CuI (10 mg, 0.05 mmol) as starting materials. Yield: 11 mg (85% based on Cu). Anal. Calcd for C13H10Cu3I3N4: C, 19.67; H, 1.27; N, 7.06%. Found: C, 20.18; H, 1.39; N, 7.10%. IR (KBr disk): 1654 (m), 1597 (m), 1559 (m), 1544 (m), 1523 (m), 1508 (m), 1487 (s), 1477 (s), 1457 (s), 1442 (w), 1365 (s), 1316 (s), 1248 (w), 1184 (w), 1160 (m), 1055 (m), 1005 (w), 970 (w), 941 (w), 880 (w), 819 (w), 777 (s), 766 (s), 726 (w), 695 (m) cm−1. Synthesis of [{Cu2(μ-I)(μ3-I)}2(μ-3,2′-pypzpy)2]n (3). Yellow crystals of 3 were prepared by a similar manner to that used for the preparation of 1 via method B, using 3,2′-pypzpy (11 mg, 0.05 mmol) and CuI (10 mg, 0.05 mmol) as starting materials. Yield: 11 mg (70% based on Cu). Anal. Calcd for C13H10Cu2I2N4: C, 25.89; H, 1.67; N, 9.29%. Found: C, 25.93; H, 1.73; N, 9.32%. IR (KBr disk): 1636 (w), 1597 (w), 1559 (w), 1527 (w), 1485 (s), 1444 (m), 1424 (w), 1370 (w), 1316 (s), 1283 (w), 1242 (w), 1165 (w), 1104 (w), 1056 (w), 989 (w), 957 (w), 915 (w), 877 (m), 832 (m), 784 (m), 752 (m), 695 (w), 656 (w), 611 (m) cm−1. Synthesis of [{Cu(μ-I)(4,2′-pypzpy)}2{Cu(μ3-I)}2]n (4). Yellow crystals of 4 were prepared by a similar manner to that used for the preparation of 1 via method A, using 4,2′-pypzpy (6 mg, 0.025 mmol) and CuI (10 mg, 0.05 mmol) as starting materials (Yield: 13 mg (87% based on Cu)), or using 4,2′-pypzpy (6 mg, 0.025 mmol) and CuI (10 mg, 0.05 mmol) as starting materials via method B (150 °C) (Yield: 12 mg (78% based on Cu)). Anal. Calcd for C13H10Cu2I2N4: C, 25.89; H, 1.67; N, 9.29%. Found: C, 26.12; H, 1.70; N, 9.33%. IR (KBr disk): 1604 (w), 1556 (m), 1479 (s), 1444 (w), 1380 (w), 1312 (m), 1271 (w), 1219 (w), 1175 (w), 1127 (w), 1085 (w), 1040 (w), 986 (w), 934 (w), 880 (w), 823 (w), 790 (w), 749 (w) 691 (s), 649 (w), 604 (w) cm−1. Synthesis of [{Cu3(μ3-I)3}(μ-2,3′-pypzpy)]n (5). Yellow crystals of 5 were prepared by a similar manner to that used for the preparation of 1 via method A, using 2,3′-pypzpy (11 mg, 0.05 mmol) and CuI (10 mg, 0.05 mmol) as starting materials. Yield: 11 mg (81% based on Cu). Anal. Calcd for C13H10Cu3I3N4: C, 19.67; H, 1.27; N, 7.06%. Found: C, 20.23; H, 1.66; N, 7.45%. IR (KBr, disk): 1599 (s), 1571 (m), 1480 (m), 1432 (s), 1384 (m), 1261 (s), 1096 (m), 1060 (w), 1020 (w), 968 (w), 807 (m), 760 (w), 729 (w), 687 (w) cm−1. Synthesis of [(CuI)(μ-2,3′-pypzpy)]2 (6). Yellow crystals of 6 were prepared by a similar manner to that used for the preparation of 1 via method B (150 °C), using 2,3′-pypzpy (11 mg, 0.05 mmol) and CuI (10 mg, 0.05 mmol) as starting materials. Yield: 16 mg (78% based on Cu). Anal. Calcd for C13H10CuIN4: C, 37.83; H, 2.44; N, C



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CuI (10 mg, 0.05 mmol) as starting materials (Yield: 17 mg (83% based on Cu)) or using 4,4′-pypzpy (11 mg, 0.05 mmol) and CuI (10 mg, 0.05 mmol) as starting materials via method A (Yield: 18.4 mg (90% based on Cu)). Anal. Calcd for C13H10CuIN4: C, 37.83; H, 2.44; N, 13.58%. Found: C, 37.22; H, 2.20; N, 13.13%. IR (KBr disk): 1062 (s), 1529 (w), 1509 (s), 1429 (m), 1370 (m), 1312 (w), 1278 (w), 1211 (m), 1049 (m), 1016 (w), 957 (m), 821 (m), 799 (m), 742 (w), 719 (m), 668 (w) cm−1. X-ray Crystallography. Each single crystal (1·MeCN, 2−6, and 11) was mounted on a glass fiber with grease and cooled in a liquid nitrogen stream at 153 K (2) or 223 K (1·MeCN, 3, 4, 5, 6, 11). Crystallographic measurements were made on a Bruker APEX-II CCD (2), or an Xcalibur Atlas Gemini (1·MeCN, 3, 4, 5, 6, 11) diffractometer by using a graphite-monochromated Mo Kα (λ = 0.71070 Å) radiation. The crystal structures of 1·MeCN, 2−6, and 11 were solved by direct methods and refined on F2 by full-matrix leastsquares techniques with SHELXTL-97 program.81,82 In 1·MeCN, each atom of one MeCN molecule was refined to half-occupancy to give acceptable thermal parameters. In the case of 2 or 4, the largest residual electron density (2.234 e·Å−3 or 1.998 e·Å−3) in the final Fourier map is close to I(2) atom (0.975 or 1.044 Å). A summary of the pertinent crystal data and structure refinement parameters for 1· MeCN, 2−6, and 11 were summarized in Table 1. The selected bond distances and angles of 1·MeCN, 2−6, and 11 are listed in Table S1.

tion or solvothermal reaction of CuI with 2,3′-pypzpy yielded one 1D polymer [{Cu3(μ3-I)3}(μ-2,3′-pypzpy)]n (5) and one binuclear complex [(CuI)(μ-2,3′-pypzpy)]2 (6), respectively. Reactions of CuI with 3,3′-pypzpy, 4,3′-pypzpy, 2,4′-pypzpy, 3,4′-pypzpy, or 4,4′-pypzpy in MeCN at room temperature produced complexes [(Cu2I2)(3,3′-pypzpy)] (7), [(CuI)(4,3′pypzpy)] (8), [{Cu(μ3-I)}2(μ-2,4′-pypzpy)2{Cu(μ-I)}2]n (9), [(CuI)(3,4′-pypzpy)] (10), and one 1D polymeric complex [(CuI)(μ-4,4′-pypzpy)]n (11), respectively. Complex 11 could also be obtained by the solvothermal reaction of CuI with 4,4′pypzpy at 150 °C. Compounds 1−11 are relatively air and moisture-stable. Complexes 2−5 and 7−11 are insoluble in common organic solvents such as CH2Cl2, MeOH, EtOH, and MeCN, and slightly soluble in DMF and DMSO. Complexes 1 and 6 are soluble in MeCN, DMF, and DMSO and slightly soluble in MeOH, EtOH, and CH2Cl2. The elemental analyses are consistent with their chemical formula. Their identities of 1−6 and 11 are finally confirmed by single-crystal X-ray crystallography. Their experimental powder X-ray diffraction (PXRD) patterns of 1−6 and 11 agree with the corresponding simulated ones from their single-crystal X-ray structures, suggesting the phase purity of these complexes (Figures S2− S8). Numerous attempts to grow crystals of 7, 8, 9, and 10 always failed. However, the PXRD patterns of the as-prepared 9 matched well with those of the simulated 4 (Figure S5), suggesting the structure of 9 is identical to that of 4, which coincides with the fact that both compounds hold very similar ligand backbones of 4,2′-pypzpy and 2,4′-pypzpy. Similar results were also observed for two Cu(II) complexes of the two analogue ligands 1,3,5-tris(1H-1,2,3-triazol-5-yl)benzene and 1,3,5-tris(tetrazol-5-yl)benzene.83,84 For 8 and 10, their observed PXRD patterns look very similar (Figure S9), suggesting they may have similar but unknown structures. Crystal Structure of [{(2,2′-pypzpy)Cu}(μ-I)]2 (1·MeCN). The asymmetric unit of 1·MeCN contains half a discrete molecule [(2,2′-pypzpy)Cu(μ-I)]2 and one MeCN lattice molecule. Complex 1 consists of two {(2,2′-pypzpy)Cu} moieties that are bridged by two μ-I atoms to form a centrosymmetric dimeric structure (Figure 1). Each Cu(I) is

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RESULTS AND DISCUSSION Syntheses of pypzpy Ligands and Complexes 1−11. As shown Scheme 1, the Ullmann condensation reactions of 2-, 3-, or 4-(1H-pyrazol-3-yl)pyridine with 2-iodopyridine, which were catalyzed by CuI/1,10-phenanthroline in the presence of excess K2CO3 at 110 °C for 24 h, generated 2,2′-(1H-pyrazole1,3-diyl)dipyridine (2,2′-pypzpy), 2-(3-(pyridin-3-yl)-1H-pyrazol-1-yl)pyridine (3,2′-pypzpy), and 2-(3-(pyridin-4-yl)-1Hpyrazol-1-yl)pyridine (4,2′-pypzpy) in high yields. The crosscoupling reactions of 2- or 3-, 4-(1H-pyrazol-3-yl)pyridine with 3-iodopyridine catalyzed by Cu2O in DMSO at 100 °C produced 2-, 3-, or 4-(1-(pyridin-3-yl)-1H-pyrazolyl)pyridine (2,3′-, 3,3′-, or 4,3′-pypzpy), respectively. Compounds 2-, 3-, and 4-(1-(pyridin-4-yl)-1H-pyrazolyl)pyridine (2,4′-, 3,4′-, or 4,4′-pypzpy) were obtained by direct solvent-free reactions of 2-, 3-, or 4-(1H-pyrazol-3-yl)pyridine with 4-iodopyridine at 190 °C with excess K2CO3. These nine organic ligands were fully characterized by elemental analysis, IR, 1H and 13C NMR spectroscopy, and mass spectrometry. These ligands are stable toward air and moisture, and freely soluble in common organic solvents such as MeOH, EtOH, MeCN, CH2Cl2, CHCl3, DMSO, and DMF. The UV−vis spectra of nine pypzpy ligands in MeCN were showed in Figure S1. All these ligands exhibit similar absorption bands. The two absorption bands at λ < 230 nm and at 240−320 nm are derived from the intraligand π → π* or n → π* electron transitions. Reaction of CuI with equimolar 2,2′-pypzpy in MeCN at room temperature, afforded one binuclear copper(I) complex [(2,2′-pypzpy)Cu(μ-I)]2 (1) in 64% yield. Solvothermal reaction of CuI and 2,2′-pypzpy in MeCN/DMF at 120 °C also produced 1 in 71%. Treatment of 3,2′-pypzpy with 1 equiv of CuI in MeCN at room temperature resulted in the formation of one 1D polymeric complex [{Cu3(μ3-I)3}(μ-3,2′-pypzpy)]n (2) in 85% yield. When we ran the reaction of CuI and 3,2′pypzpy in MeCN/DMF under the solvothermal conditions at 150 °C, one 2D polymer [{Cu2(μ-I)(μ3-I)}2(3,2′-pypzpy)2]n (3) was isolated in 70% yield. Reactions of CuI with 1 equiv of 4,2′-pypzpy in MeCN at room temperature or under solvothermal conditions gave rise to the same 1D polymeric complex [{Cu(μ3-I)}2(μ-4,2′-pypzpy)2{Cu(μ-I)}2]n (4). Reac-

Figure 1. View of a portion of the 1D chain (extended along a axis) assembled from the π−π stacking between the pyrazolyl rings of 2,2′pypzpy ligands of 1. The MeCN solvent molecules and all H atoms were omitted for clarity.

tetrahedrally coordinated by two iodides and two N atoms from one 2,2′-pypzpy ligand. The Cu(1)···Cu(1A) contact of 2.5870(7) Å (Table S1) is close to that in [Cu2I2(dfphbbtz)2] (2.5303(7) Å; dfphbbtz = 4,4′-(4,5-difluoro-1,2-phenylene)bis(1-benzyl-1H-1,2,3-triazole)),44 but shorter than those in [{(dmpzm)Cu}(μ-I)]2 (2.7412(13) Å; dmpzm = bis(3,5dimethylpyrazolyl)methane) 66 and [{Cu(μ-I)} 2 (bpp) 2 ] n (2.713(4) Å, bpp = 1,3-bis(4-pyridyl)propane),74 The mean Cu(1)-μ-I bond length (2.5942(5) Å) is shorter than those found in [{(bzdmpzm)Cu}(μ-I)]2 (2.6371(10) Å, bzdmpzm = D



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bis(4-benzyl-3,5-dimethyl-1H-pyrazolyl)methane 68 and [{Cu(μ-I)}2(bpp)2]n (2.660(2) Å).74 In 1, the Cu(1)−N(4) (pyridyl) bond distance (2.077(3) Å) is shorter than the Cu(1)−N(2) (pyrazolyl) bond length (2.145(2) Å) and those observed in [{Cu(μ-I)}2(bpp)2]n (2.066(9) Å)74 and [CuI(3pic)]4 (2.050(2) Å; 3-pic = 3-picoline).85 Each 2,2′-pypzpy has one of the two pyridyl N atoms intact and thus adopts a η1(N),η1(N′)-chelating mode to bind one Cu atoms. The adjacent dimeric molecules are stacked in a face-to-face fashion with a separation of 3.417(2) Å between the centroids of the two pyrazolyl rings of 2,2′-pypzpy ligands, leading to the formation of a 1D chain extended along the a axis (Figure 1). A further C−H···I interactions (C10−H10···I1, 3.12 Å) between the pyridyl ring of one 2,2′-pypzpy ligand in one chain and one iodide in an adjacent chain completes a 2D layer extended along the ab plane (Figure S10). Crystal Structures of [{Cu3(μ3-I)3}(μ-L)]n (L = 3,2′pypzpy (2), L = 2,3′-pypzpy (5)). Complexes 2 and 5 crystallize in the triclinic space group P1̅, and their asymmetric units contain one discrete [{Cu3(μ3-I)3}(μ-3,2′-pypzpy)] or [{Cu3(μ3-I)3}(μ-2,3′-pypzpy)] molecule. Their cell parameters are essentially identical, and so are their molecular structures (Figures 2 and S11). In 2 or 5, [{Cu3(μ3-I)3}(μ-L)]2 units are

fragment may be viewed as a double twisted-boat-shaped structure in which two twisted-boat-shaped [Cu3I3] subunits are shared with one [Cu2I2] rhomboid. The two Cu atoms on the bow are further bridged by one 3,2′-pypzpy or 2,3′-pypzpy ligand. In 2 or 5, each Cu(I) center has a tetrahedral geometry, coordinated by two μ3-I atoms and two N atoms from one 3,2′pypzpy or 2,3′-pypzpy ligand (Cu(1)), or four μ3-I atoms (Cu(2)), or three μ3-I atoms and one N atom from 3,2′-pypzpy or 2,3′-pypzpy ligand (Cu(3)). The Cu···Cu contacts of 2.630(2)-2.975(3) Å (2) and 2.6176(11)-2.9458(15) Å (5) are longer than that in 1. The mean Cu-μ3-I, Cu(1)-N(pyrazolyl), and Cu(3)-N(pyridinyl) bond distances in 2 and 5 are normal. Each 3,2′-pypzpy or 2,3′-pypzpy adopts a μ−η1(N),η1(N′),η1(N″)-chelating/bridging mode to bind two Cu atoms via three Cu−N bonds. In 2, the 1D chains are further interlinked by the π−π interactions of the two pyridyl rings (3.496(7) Å) and two pyrazolyl rings (3.472(8) Å) of 3,2′-pypzpy ligands, forming a 3D architecture (Figure S12). Crystal Structure of [{Cu2(μ-I)(μ3-I)}2(3,2′-pypzpy)2]n (3). The asymmetric unit of 3 contains half a discrete [{Cu2(μ-I)(μ3-I)}2(3,2′-pypzpy)2] molecule. It holds a 2D sheet structure (extended along the [101] plane) in which each chairlike [Cu2(μ-I)(μ3-I)]2 fragment, surrounded by four independent 3,2′-pypzpy ligands, works as a four-connecting node to link the neighboring 4 equivalent ones by two Cu− N(pyridyl) and two pairs of chelating Cu−N bonds (Figure 3). Each Cu(I) is tetrahedrally coordinated by one N of 3,2′pypzpy ligand and three μ3-I atoms (Cu(1)) or two iodides and two N atoms from one 3,2′-pypzpy ligand (Cu(2)). Each 3,2′pypzpy adopts a μ−η1(N),η1(N′),η1(N″)-chelating/bridging mode to bind two Cu atoms via three Cu−N bonds. In the crystal of 3, each 2D sheet is bridged by π−π interactions of the two pyridyl rings (3.592(5) Å) of 3,2′-pypzpy ligands, forming a 3D net (Figure S13). This network is further stabilized by some pertinent H-bonding interactions such as C(6)−H···I(1) (3.09 Å), C(8)−H···I(1) (3.21 Å), C(7)−H···I(2) (3.15 Å), C(10)−H···I(1) (3.36 Å), C(3)−H···I(1) (3.02 Å), and C(3)− H···I(1) (3.35 Å). Crystal Structure of [{Cu(μ3-I)}2(4,2′-pypzpy)2{Cu(μI)}2]n (4). The asymmetric unit of 4 has half a discrete

Figure 2. View of a section of the displaced staircase chain of 2 with 50% thermal ellipsoids. All H atoms were omitted for clarity.

interlinked to adjacent ones by two Cu-μ3-I bonds, forming a unique 1D displaced staircase chain [{Cu3(μ3-I)3}(μ-3,2′pypzpy)]n extending along the b axis. Each [{Cu3(μ3-I)3}]2

Figure 3. View of the 2D network of 3 with a labeling scheme and 50% thermal ellipsoids. All H atoms were omitted for clarity. E



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η1(N″) chelating/bridging mode to bind two Cu atoms via three Cu−N bonds. Each Cu atom is tetrahedrally coordinated by one I and three N atoms from two 2,3′-pypzpy ligands. Each [(CuI)(μ-2,3′-pypzpy)]2 molecule is further interconnected via π−π interactions (3.767(3) Å) of the two pyridyl rings of 2,3′pypzpy ligands, forming one 1D chain extended along the c axis (Figure 5). Such chains are linked by four H-bonding interactions between I1 and the pyrazolyl ring with C1 (3.04 Å), between I1 and the pyridyl group with C6 (3.26 Å), between I1 and the pyridyl group with C10 (3.32 Å), and between I1 and the pyridyl group with C12 (3.22 Å) to form a 3D H-bonded network (Figure S15). Crystal Structure of [(CuI)(μ-4,4′-pypzpy)]n (11). The asymmetric unit of 11 possesses half a [(CuI)(μ-4,4′-pypzpy)] molecule. This compound has a 1D chain (extended along [1̅, 0, 1] or [1, 0, 1] direction), in which each [CuI] unit is bridged by 4,4′-pypzpy ligands (Figure 6). Each Cu(I) is trigonally coordinated by two N atom from two μ-4,4′-pypzpy ligands and one I− anion. Each 4,4′-pypzpy keeps its N(pyrazolyl) intact, and thus takes a μ−η1(N),η1(N′)-bridging mode to bind two Cu atoms via two Cu−N bonds. Such a chain is combined with its neighboring ones via the π−π interactions of the pyridyl ring and pyrazolyl ring (3.781(7) Å) to form a 2D layer structure (Figure S16). The layers are further held together by hydrogen bonding interactions like C(4)-H···I(1) (3.19 Å) and C(4)-H···I(1) (3.19 Å) to afford a 3D H-bonded structure (Figure S17). According to the aforementioned X-ray analysis, the different coordination sites of the pypzpy ligands do have a significant influence on their coordination modes, the coordination number of Cu(I) atom, the [CunIn] motifs, and the final structures. Among 1−6, 9, and 11, only 1 has its 2,2′-pypzpy ligand working as a chelating bidentate ligand. This is understandable because this ligand has each of two N atoms of the 2-pyridyl groups to combine the pyrazolyl N atom to chelate one Cu(I) center while the other 2-pyridyl N atom remains uncoordinated due to the steric hindrance. For 2−6 and 9, those bearing one 2-pyridyl and the other 3- or 4-pyridyl groups, that is, 3,2′-pypzpy, 2,3′-pypzpy, 4,2′-pypzpy, and 2,4′pypzpy, all exhibit a μ−η1(N),η1(N′),η1(N″)-chelating/bridging coordination fashion. These ligands can use one 2-pyridyl N and one pyrazolyl N atom to chelate one Cu(I) while the 3- or 4-pyridyl N atom bridges the other Cu(I). For 11, its 4,4′pypzpy takes a μ−η1(N)-η1(N)-bridging mode, and the 4pyridyl N atom binds one Cu(I) while the one pyrazolyl N atom remains intact. Each Cu(I) adopts a tetrahedral coordination sphere in 1−6 and 9 or a trigonal coordination geometry in 11. Regarding the formation of [CunIn] motifs, reactions of CuI with 4,4′-pypzpy or 2,2′-pypzpy produce small [CunIn] units such as monomeric unit [CuI] (11), dimeric unit [Cu2I2] (1). When 2,3′-pypzpy, 2,4′-pypzpy, 3,2′-pypzpy, or 4,2′-pypzpy is employed in the reaction system, more complicated chain [CunIn] units are formed at room temperature, such as 1D displaced staircase chain [Cu3(μ3-I)3]n (2 and 5), staircase chain [Cu2(μ3-I)2]n mixed with two zigzag chains

[{Cu(μ3-I)}{μ-(4,2′-pypzpy)}{Cu(μ-I)}] molecule. This complex has an unprecedented triple-chain (extended along the b direction), in which the internal 1D staircase chain [Cu2(μ3I)2]n is connected with two zigzag chains [Cu(μ-I)]n via 4,2′pypzpy linkers (Figure 4). Each Cu(I) is tetrahedrally

Figure 4. View of a section of the triple chain of 4 looking along the b axis. All H atoms are omitted for clarity.

coordinated by two μ-I and two N atoms from one 4,2′pypzpy ligand (Cu(1)) or one N of 4,2′-pypzpy ligand and three μ3-I atoms (Cu(2)). Each 4,2′-pypzpy adopts a μ−η1(N),η1(N′),η1(N″)-chelating/bridging mode to bind two Cu atoms via three Cu−N bonds. Each 1D triple-chain is further bridged by four H-bonding interactions including C(3)−H···I(1) (3.35 Å), C(5)−H···I(1) (3.22 Å), C(2)−H··· I(2) (3.23 Å), and C(13)−H···I(2) (3.12 Å) to form a 3D Hbonded structure (Figure S14). Crystal Structure of [(CuI)(μ-2,3′-pypzpy)]2 (6). The asymmetric unit of 6 contains half a [(CuI)(μ-2,3′-pypzpy)] molecule. This molecule consists of two {CuI} units interconnected by two μ-2,3′-pypzpy ligands, forming a centrosymmetric 12-membered metallocycle structure (Figure 5). Each 2,3′-pypzpy ligand in 6 takes a μ−η1(N),η1(N′)-

Figure 5. View of a segment of the 1D chain assembled by the π−π stacking interactions between the pyridyl rings of 2,3′-pypzpy ligands in 6. All H atoms were omitted for clarity.

Figure 6. View of a portion of the 1D chain of 11 with a labeling scheme and 50% thermal ellipsoids. All H atoms are omitted for clarity. F



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emission energy of each Cu(I) complex is much lower than that of the corresponding pypzpy ligand (Figure S17), which eliminates the intraligand π−π* transitions. Some previous works show that the emission energies of copper(I)-iodide complexes are strongly affected by the heterocyclic organic ligands and [CunIn] motifs. The origins of the luminescent emissions could be assigned to be iodide-to-copper(I) chargetransfer (XMCT), ligand-to-metal charge transfer (LMCT), halogen-to-ligand charge transfer (XLCT), cluster-centered (CC*) transition, or the admixture of more than one of the above.13,14,26,36,44,85−90 For example, the emission of [Cu2(μI)2(py)4] (py = pyridine) is mainly attributed to both CC* transition and XLCT.88 For 1, the emission maxima at 595 nm is red-shifted relative to those of the dimeric complex [Cu2(μI)2(dfphbbtz)2] (λmaxem = 495 nm),44 [(bzdmpzm)Cu(μ-I)]2 (λmaxem = 519 nm),68 [Cu2(μ-I)2(py)4] (λmaxem = 517 nm),88 and [Cu2I2]-based complexes [Cu2(μ-I)2(bpp)2]n (λmaxem = 507 nm).74 The emission origin of 1 may thus be assigned to the combination of cluster-centered transition, ligand-to-metal charge transfer, and iodide-to-ligand charge transfer. In 2 and 3, the ligands are the same and Cu···Cu distances are similar. However, the emission peak of 2 is 11 nm blue-shifted relative to that of 3, which may be ascribed to the presence of stronger π−π interactions in 2. In fact, the intermolecular π−π contacts of the two pyridyl rings (3.496(7) Å) and two pyrazolyl rings (3.472(8) Å) of 3,2′-pypzpy ligands in 2 are shorter than that of the two pyridyl rings (3.592(5) Å) of 3,2′-pypzpy ligands in 3. Such stronger π−π interactions could modify the energy level of the lowest unoccupied molecular orbital (LUMO).44 For 5 and 6 with 2,3′-pypzpy ligand, the emission blue shift from 6 to 5 (31 nm) may be due to the fact that the Cu···Cu interactions in 5 (2.6176(11) Å-2.9458(15) Å) are stronger than that of 6 (5.275(5) Å). Although the structures of 2 and 5 (or 8 and 10) are almost the same, the emission maximum of 5 or 10 is somewhat red-shifted relative to the corresponding one of 2 and 8, which might be attributed to the different ligands.89 The ligands can modify the energy level of the molecular orbitals (MOs). Upon excitation at 332 or 365 nm, 4 and 9 produced a broad emission with the maxima at 637 and 670 nm, respectively (Figure 7). The emissions of 4 and 9 appear at a much low energy with a large Stokes shift of 305 nm. As described above, the structures of 4 and 9 contain two different [CunIn] units. The low-energy emissions associated with large Stokes shifts have been commonly observed for Cu(I)-cluster based complexes.90 The emission origins of 4 and 9 might be derived from an excited state of mixed XMCT and coppercluster-centered d → s,p character. As discussed above, the formation of the [CunIn] motifs largely depends on the coordination site of the pypzpy ligands. The [CunIn] fragments along with the pypzpy ligands cooperatively exert a significant influence on the luminescent properties of the final products.

[Cu(μ-I)]n (4 and 9). In addition, the reaction temperature seems to affect the formation of [CunIn] motifs when using the above four ligands. At 120 or 150 °C, the 3D framework of the bulk CuI is cleaved into discrete [CunIn] motifs such as the chairlike unit [Cu4(μ-I)2(μ3-I)2] (3) and the monomeric unit [CuI] (6). These resulting units are further interconnected via these pypzpy ligands to form different [Cu n I n ]-based topological structures. For the [CuI]-based complexes 1, 6, and 11, the intact 2′-pyridyl group of 2,2′-pypzpy in 1 drives the iodide to bridge the other Cu(I) to form a dimeric structure while the 3′-pyridyl group of 2,3′-pypzpy in 6 binds the other Cu(I) to give another dimeric structure. However, the [CuI] unit in 11 is linked by 4- and 4′-pyridyl groups of 4,4′-pypzpy to form a 1D chain structure. For 3, the independent chairlike unit [Cu4(μ-I)2(μ3-I)2] is surrounded by four 3,2′-pypzpy ligands to give [Cu4(μ-I)2(μ3-I)2(3,2′-pypzpy)4], which is connected to the four neighboring ones via two Cu−N(3pyridyl) and two pairs of chelating Cu−N bonds to yield a 2D network. For the chain [CunIn]-based complexes 2, 4, 5, and 9, the displaced staircase chains [Cu3(μ3-I)3]n are covered by 3,2′pypzpy or 2,3′-pypzpy ligands (2 and 5), while two zigzag chains [Cu(μ-I)]n are connected to the central 1D staircase chain [Cu2(μ3-I)2]n via 4- or 4′-pyridyl groups of 4,2′-pypzpy or 2,4′-pypzpy to form a 1D triple chain (4 and 9). Photoluminescent Properties. The photoluminescent properties of 1−11 in the solid state along with nine pypzpy ligands in MeCN solution at room temperature are examined. Complexes 1−11 and nine pypzpy ligands show strong photoluminescence upon UV light irradiation. The emission spectra of the 11 Cu(I) complexes have been recorded in Figure 7. Upon excitation at ca. 300 nm, the emission maxima

Figure 7. Emission spectra of 1−11 in the solid state at room temperature.

of these ligands are located in the range of 310−335 nm (Figure S17). The emission of these pypzpy ligands may be originated from the intraligand π−π* transitions. Complexes 1−11 exhibit broad emissions between 470 and 800 nm with maxima at ca. 595 nm (1), 557 nm (2), 568 nm (3), 637 nm (4), 587 nm (5), 618 nm (6), 565 nm (7), 588 nm (8), 670 nm (9), 617 nm (10), and 575 nm (11); excited at 340 nm (1), 372 nm (2), 439 nm (3), 332 nm (4), 382 nm (5), 370 nm (6), 381 nm (7 and 8) 365 nm (9), 408 nm (10), and 398 nm (11), respectively. The order of emission energy of these complexes decreases in the order of 2 < 3, 7 < 11 < 5, 8 < 1 < 6, 10 < 4 < 9. Such a blue shift from 2 to 9 may be ascribed to the existence of the different ligands, the different [CunIn] units, aromatic πstacking interactions and even their topological structures. The

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CONCLUSIONS In summary, the assembly of copper(I) iodide and nine pypzpy ligands with different coordination sites gave rise to 11 [CunIn]based coordination complexes 1−11, among which the structures of 1−6 and 11 are structurally confirmed. When these ligands bind at Cu(I) centers, their different coordination sites lead to the formation of different coordination modes: chelating (2,2′-pypzpy (1)), μ−η1(N),η1(N′)-η1(N″) (2,3′pypzpy (2, 3) 2,4′-pypzpy (4), 3,2′-pypzpy (5, 6), 4,2′-pypzpy (9)), and μ−η1(N)-η1(N′) (11). Correspondingly, various [CunIn] motifs such as the rhomboid binuclear [Cu(μ-I)]2 unit G



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in 1, displaced staircase chains [Cu3(μ3-I)3]n in 2 and 5, the staircase chain [Cu2(μ3-I)2]n and zigzag chains [Cu(μ-I)]n in 4 and 9, and the [CuI] unit in 11 are generated at room temperature. While the discrete [CuI] unit (6 and 11) and the chairlike unit [Cu4(μ-I)2(μ3-I)2] (3) are produced at a higher temperature. In addition, these complexes also show remarkable differences in their luminescent emission responses, which is due to the different pypzpy ligands, the different [CunIn] units, and even their [CunIn]-based frameworks. These results demonstrated that the coordination sites of pypzpy ligands have a profound effect on their coordination modes and the generation of the [CunIn] units and the [CunIn]-based complexes along with their luminescent properties, which are useful for the rational design and assembly of [CunIn]-based complexes as advanced optoelectronic materials.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acs.cgd.5b01721. Crystal structural data for 1·MeCN, 2, 3, 4 (CCDC 1025427, 1025428, 1025300, 1025301) and for 5, 6, 11 (CCDC 1435553−1435555) in CIF. The 1H and 13C NMR spectra of all pypzpy ligands, the PXRD patterns for 1−11, Crystal data and structure refinement parameters for 1·MeCN, 2−6, and 11, and the selected bond lengths and angles of 1−6 and 11 (PDF) Accession Codes

CCDC 1025300−1025301, 1025427−1025428, and 1435553− 1435555 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge via www.ccdc.cam.ac.uk/data_request/cif, or by emailing data_ [email protected], or by contacting The Cambridge Crystallographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: +44 1223 336033.

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AUTHOR INFORMATION

Corresponding Authors

*E-mail: [email protected]. Fax: 86-512-65880328. Tel: 86512-65882865. *E-mail: [email protected]. Notes

The authors declare no competing financial interest.

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ACKNOWLEDGMENTS This work is financially supported by the National Natural Science Foundation of China (Grant Nos. 21373142, 21171125, 21471108, and 21531006), the State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences (2015kf-07), and the State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials. J. P. Lang is grateful to the funds from the “333” Project of Jiangsu Province, the Priority Academic Program Development of Jiangsu Higher Education Institutions, and the “SooChow Scholar” Program of Soochow University.

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Ligand Coordination Site-Directed Assembly of Copper(I) Iodide

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