化学·生活·社会
分子间的非共价相互作用：σ -穴键和π -穴键
崔瑜瑾1 , 晋卫军2
1. 长治学院化学系 山西长治 046011;
Intermolecular Noncovalent Interactions: σ -Hole Bond and π -Hole Bond
CUI Yu-Jin1 , JIN Wei-Jun2
1. Department of Chemistry, Changzhi University, Changzhi 046011, China;
摘要： 第四到第七主族元素以及惰性气体元素可以作为电子受体位点形成分子间吸引性的非共价键合作用。这些电子受体位点，即缺电子密度的位点，大多情况下具有正的分子表面静电势，可以将其分为2类。沿着σ共价键键轴延伸方向原子的外围中心具有正的分子表面静电势的区域称之为σ-穴。而垂直于分子σ-骨架平面具有正的分子表面静电势区域称之为π-穴。σ-穴和π-穴与富电性位点之间吸引性的相互作用分别称之为σ-穴键和π-穴键。σ-穴键倾向于180°，而π-穴键倾向于90°。按照元素周期表族的名称，σ-穴键又分为碳素键、氮素键、氧素键、卤键、惰素键等。可见流行的卤键只是σ-穴键的一个子集。π-穴键分类显得复杂些，可简单分为单原子和多原子π-穴键。
关键词： σ -穴键π -穴键卤键 ,
氧素键 ,
氮素键 ,
碳素键 ,
惰素键
基金资助: 国家自然科学基金资助，“卤键和氢键、π-π堆积作用共驱组装功能化复合晶体”（90922023，20675013）
通讯作者:
晋卫军
E-mail: wjjin@bnu.edu.cn
引用本文:
崔瑜瑾, 晋卫军. 分子间的非共价相互作用：σ -穴键和π -穴键[J]. 化学教育（中英文）, 2018, 39(14): 1-11
[1]
Alcock N W. Adv. Inorg. Chem. Radiochem., 1972, 15(1):1-58
[2]
Haiduc I. "Secondary bond" in "Encyclopedia of Supramolecular Chemistry". New York:Marcel Dekker, Inc., 2004:1215-1224
[3]
Brammer L. Faraday Discuss., 2017, 203:485-507
[4]
(a)IUCr 2011 Satellite Workshop. Sigüenza, 2011; (b)The 1st International Symposium on Halogen Bonding (ISXB-1) in Porto Cesareo. Lecce, 2014; (c)The 2nd International Symposium on Halogen Bonding (ISXB-2). Göthenburg, 2016; (d)The 3rd International Symposium on Halogen Bonding (ISXB-3) and an International Workshop as a satellite event ofISXB-3:Interactions Involving Group 14-16 Elements as Electrophilic Sites:A World Parallel to Halogen Bond. Greenville, 2018
[5]
Clark T, Hennemann M, Murray J S. J. Mol. Model., 2007, 13(2):291-296
[6]
Murray J S, Lane P, Clark T, et al. J. Mol. Model., 2012, 18(2):541-548
[7]
Pang X, Wang H, Zhao X R, et al. CrystEngComm, 2013, 15(14):2722-2730
[8]
Wang H, Wang W, Jin W J. Chem. Rev., 2016, 116(9):5072-5104
[9]
Politzer P, Murray J S. J. Comput. Chem.,2018, 39(9):464-471
[10]
Desiraju G R, Ho P S, Kloo L, et al. Prue Appl. Chem., 2013, 85(8):1711-1713
[11]
Quiñonero D, Garau C, Rotger C, et al.Angew. Chem. Int. Ed., 2002, 41(18):3389-3392
[12]
Wang D X, Wang M X. J. Am. Chem. Soc., 2013, 135(2):892-897
[13]
Giese M, Albrecht M, Rissanen K. Chem. Rev.,2015, 115(16):8867-8895
[14]
Clark T, Politzer P, Murray J S. WIREs Comput. Mol. Sci., 2015, 5(2):169-177
[15]
Politzer P, Murray J S, Clark T. Top Curr. Chem., 2015, 358:19-42
[16]
Gilday L C, Robinson S W, Barendt T A, et al. Chem. Rev., 2015, 115(15):7118-7195
[17]
Cavallo G, Metrangolo P, Milani R, et al. Chem. Rev., 2016, 116(4):2478-2601
[18]
Gao H Y, Shen Q J, Zhao X R, et al. J. Mater. Chem., 2012, 22(12):5336-5343
[19]
Gao H Y, Zhao X R, Wang H, et al. Cryst. Growth. Des., 2012, 12(9):4377-4387
[20]
Shen Q J, Wei H Q, Zou W S, et al. CrystEngComm, 2012, 14(3):1010-1015
[21]
Pang X, Wang H, Wang W, et al. Cryst. Growth Des., 2015, 15(10):4938-4945
[22]
Beyeh N K, Pan F, Rissanen K. Angew. Chem., 2015, 127(25):7411-7415
[23]
Beyeh N K, Valkonen A, Bhowmik S, et al. Org. Chem. Front., 2015, 2(4):340-345
[24]
Metrangolo P, Meyer F, Pilati T, et al. Chem. Commun., 2008(14):1635-1637
[25]
Liu R, Wang H, Jin W J. Cryst. Growth Des.,2017, 17(6):3331-3337
[26]
Shen Q J, Jin W J.Phys. Chem. Chem. Phys., 2011, 13(30):13721-13729
[27]
Caballero A, Zapata F, White N G, et al. Angew. Chem. Int. Ed., 2012, 51(8):1876-1880
[28]
Zapata F, Caballero A, White N G, et al. J. Am. Chem. Soc., 2012, 134(28):11533-11541
[29]
Wang H, Zhao X R, Jin W J. Phys. Chem. Chem. Phys., 2013, 15(12):4320-4328
[30]
Wang D X, Zheng Q Y, Wang Q Q, et al. Angew. Chem. Int. Ed., 2008, 47(39):7485-7488
[31]
Li S, Fa S X, Wang Q Q, et al. J. Org. Chem., 2012, 77(4):1860-1867
[32]
Hafezi N, Holcroft J M, Hartlieb K J,et al. Angew. Chem. Int. Ed., 2015, 54(2):456-461
[33]
Wang H, Li C, Wang W, et al. Phys. Chem. Chem. Phys., 2015, 17(32):20636-20646
[34]
Zhao X R, Shen Q J, Jin W J. Chem. Phys. Lett., 2013, 566:60-66
[35]
Pang X, Jin W J. New J. Chem., 2015, 39(7):5477-5483
[36]
Yan X Q, Zhao X R, Wang H, et al. J. Phys. Chem. B, 2014, 118(4):1080-1087
[37]
Wang W, Ji B, Zhang Y. J. Phys. Chem. A, 2009, 113(28):8132-8135
[38]
Huynh H T, Jeannin O, Fourmigué M. Chem. Commun., 2017, 53(60):8467-8469
[39]
Liu Y H, Zhang Z, Feng S Y, et al. J. Am. Chem. Soc., 2017, 139(9):3356-3359
[40]
Bauza A, Mooibroek T J, Frontera A. ChemPhysChem, 2015, 16(12):2496-2517
[41]
Bauzá A, Ramis R, Frontera A. J. Phys. Chem. A, 2014, 118(15):2827-2834
[42]
Alkorta I, Elguero J, Del Bene J E. J. Phys. Chem. A, 2013, 117(40):10497-10503
[43]
Wang Y H, Zeng Y L, Li X Y, et al. Struct. Chem., 2016, 27(5):1427-1437
[44]
Bauzá A, Mooibroek T J, Frontera A. Angew. Chem. Int. Ed., 2013, 52(47):12317-12321
[45]
Quiñonero D. Phys. Chem. Chem. Phys., 2017, 19(23):15530-15540
[46]
Bauzá A, Frontera A. Crystals, 2016, 6(1):26-38
