基于功能化6-甲氧羰基-2,2′-联吡啶配体的铜(Ⅰ)铁(Ⅱ)异金属双核配合物（英文）
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摘要
以[Cu(CH_3CN)_4]ClO_4、6-甲氧羰基-2,2′-联吡啶(mbpy)、6-甲氧羰基-4,4′-二甲基-2,2′-联吡啶(mmbpy)和1,1′-双(二苯基膦)二茂铁(dppf)为起始原料,合成得到了2个新的铜(Ⅰ)铁(Ⅱ)异金属双核配合物:[Cu(mbpy)(dppf)]ClO_4·CH_2Cl_2(1)和[Cu(mmbpy)(dppf)]ClO_4(2)。X射线单晶衍射分析表明,配合物1和2均为铜(Ⅰ)铁(Ⅱ)异金属双核配合物,并且均表现为四配位变形四面体构型。配合物1和2在330~520 nm波长范围有一个弱的低能量宽吸收峰,其主要来源于金属到配体的电荷转移跃迁(MLCT)。由于1,1′-双(二苯基膦)二茂铁的引入,配合物1和2常温下在溶液和固态时均未检测到任何发光。
Two new Cu (Ⅰ) Fe (Ⅱ) heterobimetallic complexes, [Cu(mbpy)(dppf)]ClO_4·CH_2 Cl_2(1) and [Cu(mmbpy)(dppf)]ClO_4(2), were synthesized by using [Cu(CH_3 CN)_4]ClO_4, 6-methoxycarbonyl-2,2′-bipyridine(mbpy), 6-methoxycarbonyl-4,4′-dimethyl-2,2′-bipyridine(mmbpy), and 1,1′-bis(diphenylphosphino)ferrocene(dppf) as the starting materials. As revealed by single-crystal X-ray diffraction analysis, complexes 1 and 2 are all Cu (Ⅰ) Fe (Ⅱ)heterobimetallic species and exhibit tetra-coordinated and distorted tetrahedral configuration. Complexes 1 and 2 all show a weak low-energy broad absorption in the wavelength range of 330~520 nm, which is mainly assigned to metal-to-ligand charge-transfer(MLCT) transition. No emission is detected in solution and solid states at room temperature for 1 and 2, due to the introduction of 1,1′-bis(diphenylphosphino)ferrocene. CCDC: 1835415, 1;1835416, 2.
Two new Cu (Ⅰ) Fe (Ⅱ) heterobimetallic complexes, [Cu(mbpy)(dppf)]ClO_4·CH_2 Cl_2(1) and [Cu(mmbpy)(dppf)]ClO_4(2), were synthesized by using [Cu(CH_3 CN)_4]ClO_4, 6-methoxycarbonyl-2,2′-bipyridine(mbpy), 6-methoxycarbonyl-4,4′-dimethyl-2,2′-bipyridine(mmbpy), and 1,1′-bis(diphenylphosphino)ferrocene(dppf) as the starting materials. As revealed by single-crystal X-ray diffraction analysis, complexes 1 and 2 are all Cu (Ⅰ) Fe (Ⅱ)heterobimetallic species and exhibit tetra-coordinated and distorted tetrahedral configuration. Complexes 1 and 2 all show a weak low-energy broad absorption in the wavelength range of 330~520 nm, which is mainly assigned to metal-to-ligand charge-transfer(MLCT) transition. No emission is detected in solution and solid states at room temperature for 1 and 2, due to the introduction of 1,1′-bis(diphenylphosphino)ferrocene. CCDC: 1835415, 1;1835416, 2.
引文
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[4] Chen J L, Chang S Y, Chi Y, et al. Chem. Asian J., 2008,3:2112-2123
[5] Chen J L, Chi Y, Chen K, et al. Inorg. Chem., 2010,49:823-832
[6] Chen J L, Wu Y H, He L H, et al. Organometallics, 2010,29:2882-2891
[7] Armaroli N, Accorsi G, Cardinali F, et al. Top. Curr. Chem.,2007,280:69-115
[8] Zhang J, Xiong R G, Zuo J L, et al. Chem. Commun., 2000,36:1495-1496
[9] Wang J H, Li M, Li D. Chem. Sci., 2013,4:1793-1801
[10]Chen Y Q, Li G R, Chang Z, et al. Chem. Sci., 2013,4:3678-3682
[11]Li J C, Li H X, Li H Y, et al. Crystal. Growth Des., 2016,16:1617-1625
[12]He L H, Luo Y S, Di B S, et al. Inorg. Chem., 2017,56:10311-10324
[13]Chen J L, Zeng X H, Luo Y S, et al. Dalton Trans., 2017,46:13077-13087
[14]JIN Dou-Man(金斗满), YANG Rui-Na(杨瑞娜), WANG Dong-Mei(王冬梅), et al. Chinese J. Inorg. Chem.(无机化学学报), 2000,16(2):335-340
[15]ZHANG Zhong(张众), LIU Ji-Zhong(刘积中), GAO Peng(高鹏), et al. Chinese J. Inorg. Chem.(无机化学学报), 2012,28(1):195-200
[16]HUANG Yan-Hong(黄廷洪), YAN Jie(颜杰), YANG Hu(杨虎), et al. Chinese J. Inorg. Chem.(无机化学学报), 2015,31(12):2393-2400
[17]Young D J, Chien S W, Hor T S A. Dalton Trans., 2012,41:12655-12665
[18]Kubas G J, Monzyk B, Crumbliss A L. Inorg. Synth., 1979,19:90-92
[19]Norrby T, BOrje A, Zhang L, et al. Acta Chem. Scand., 1998,52:77-85
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[21]ZENG Xue-Hua(曾雪花), LUO Yan-Sheng(罗燕生), HE LiHua(何丽华), et al. Chinese J. Inorg. Chem.(无机化学学报),2017,33(10):1810-1816
[22]XIA Yong(夏勇), ZENG Xue-Hua(曾雪花), LUO Yan-Sheng(罗燕生), et al. Chinese J. Inorg. Chem.(无机化学学报),2016,32(11):2012-2016
[23]Chen J L, Fu X F, Wang J Y, et al. Inorg. Chem. Commun.,2015,53:88-91
[24]Zhang Q, Zhou Q, Cheng Y, et al. Adv. Mater., 2004,16:432-436
[25]Chen J L, Cao X F, Gu W, et al. Inorg. Chem. Commun.,2012,15:65-68
[26]He L H, Chen J L, Zhang F, et al. Inorg. Chem. Commun.,2012,21:125-128
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[32]Li M, Guo Z, Zhu W, et al. Chem. Commun., 2015,51:1293-1296