系列Ag-Ln配位聚合物的合成、结构及发光性能
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摘要
采用水热合成法,以吡嗪-2-羧酸(2-Hpzc)、3,5-吡啶二羧酸(3,5-H_2PDA)和草酸(H_2ox)为配体,合成9种Ag-Ln配位聚合物:{[LnAg(2-pzc)_2(ox)]·H_2O}_n(Ln=Pr(1),Nd(2),Sm(3),Eu(4)),[LnAg(3,5-PDA)(ox)(H_2O)]_n(Ln=Pr(5),Nd(6)),[LnAg(3,5-PDA)(3,5-HPDA)(ox)_(0.5)(H_2O)_2]_n(Ln=Sm(7),Dy(8),Ho(9))。配位聚合物1～4是同构的,由2-pzc~-和ox~(2-)连接,而配位聚合物5～9是以3,5-PDA~(2-)和ox~(2-)为桥联配体,均呈现3D网状结构。光物理性能研究表明配位聚合物均表现出Ln(Ⅲ)的特征发射,这可归因于Ag-配体部分(d-block)的敏化作用。另外,在晶体场和Ag(1)离子4d轨道的共同作用下,Ln(Ⅲ)离子的4f轨道被调谐,使部分能级发生明显的位移,表现为相应NIR发射带的位移,在其UV-Vis-NIR吸收光谱中可以得到佐证。
Using pyrazine-2-carboxylic acid(2-Hpzc),3,5-pyridinedicarboxylic acid(3,5-H_2PDA)and oxalic acid(H_2ox)as ligands,nine Ag-Ln coordination polymers are synthesized by hydrothermal methods:{[LnAg(2-pzc)_2(ox)]·H_2O}_n(Ln=Pr(1),Nd(2),Sm(3),Eu(4)),[LnAg(3,5-PDA)(ox)(H_2O)]_n(Ln=Pr(5),Nd(6)),[LnAg(3,5-PDA)(3,5-HPDA)(ox)_(0.5)(H_2O)_2]_n(Ln=Sm(7),Dy(8),Ho(9)).All of them possess the 3D network structure,i.e.,coordination polymers 1～4 are isomorphic and connected by 2-pzc~-and ox~(2-),while coordination polymers 5～9 use 3,5-PDA~(2-)and ox~(2-)as bridging ligands.Photophysical properties of these coordination polymers are studied,and they show characteristic emissions of corresponding Ln(Ⅲ)ions which should be attributed to the sensitization of the Agligand section(d-block).In addition,under the co-action of crystal field and 4d orbits of Ag(1)ion,the 4f orbits of Ln(Ⅲ)ions are tuned and cause obvious shift of partial energy levels,which present shifts of the corresponding NIR emission bands and can be corroborated in their UV-Vis-NIR absorption spectra.
Using pyrazine-2-carboxylic acid(2-Hpzc),3,5-pyridinedicarboxylic acid(3,5-H_2PDA)and oxalic acid(H_2ox)as ligands,nine Ag-Ln coordination polymers are synthesized by hydrothermal methods:{[LnAg(2-pzc)_2(ox)]·H_2O}_n(Ln=Pr(1),Nd(2),Sm(3),Eu(4)),[LnAg(3,5-PDA)(ox)(H_2O)]_n(Ln=Pr(5),Nd(6)),[LnAg(3,5-PDA)(3,5-HPDA)(ox)_(0.5)(H_2O)_2]_n(Ln=Sm(7),Dy(8),Ho(9)).All of them possess the 3D network structure,i.e.,coordination polymers 1～4 are isomorphic and connected by 2-pzc~-and ox~(2-),while coordination polymers 5～9 use 3,5-PDA~(2-)and ox~(2-)as bridging ligands.Photophysical properties of these coordination polymers are studied,and they show characteristic emissions of corresponding Ln(Ⅲ)ions which should be attributed to the sensitization of the Agligand section(d-block).In addition,under the co-action of crystal field and 4d orbits of Ag(1)ion,the 4f orbits of Ln(Ⅲ)ions are tuned and cause obvious shift of partial energy levels,which present shifts of the corresponding NIR emission bands and can be corroborated in their UV-Vis-NIR absorption spectra.
引文
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[6] Li X F, Huang Y B, Zhao H J, et al. Inorg. Chem. Commun.,2012,23:132-136
[7] Feng X, Feng Y Q, Chen J J, et al. Dalton Trans., 2015,44(2):804-816
[8] Liu X W, Guo R, Liu H, et al. RSC Adv., 2015,5(20):15059-15068
[9] Maity M, Majee M C, Kundu S, et al. Inorg. Chem., 2015,54(20):9715-9726
[10]LIU Yang(刘杨), WANG Zhen-Ping(王振平), WANG QingLun(王庆伦), et al. Chinese J. Inorg. Chem.(无机化学学报),2018,34(8):1448-1454
[11]Wang Y, Wang X G, Yuan B, et al. Inorg. Chem., 2015,54(9):4456-4465
[12]LIN Yu-Qing(林雨青), GAO Min(高敏), ZHANG Hui(张辉),et al. Chinese J. Inorg. Chem.(无机化学学报), 2018,34(9):1600-1609
[13]Yang X P, Wang S Q, Zang L J, et al. J. Mater. Chem. C,2016,4:1589-1593
[14]Visinescu D, Alexandru M G, Madalan A M, et al. Dalton Trans., 2015,44:16713-16727
[15]Blacque O, Amjad A, Caneschi A, et al. New J. Chem.,2016,40:3571-3577
[16]Ran X R, Wang N, Xie W P, et al. J. Solid State Chem.,2015,225:24-30
[17]Zhang L, Zhao L, Zhang P, et al. Inorg. Chem., 2015,54:11535-11541
[18]Armelao L, Quici S, Barigelletti F, et al. Coord. Chem. Rev.,2010,254(5):487-505
[19]Hasegawa Y, Wada Y, Yanagida S. J. Photochem. Photobiol.C:Photochem. Rev., 2004,5(3):183-202
[20]Liu Z H, Qiu Y C, Li Y H, et al. Polyhedron, 2008,27:3493-3499
[21]Li Z Y, Dai J W, Wang N. Cryst. Growth Des., 2010,10(6):2746-2751
[22]Liu G X. J. Rare Earths, 2012,30(7):716-720
[23]Zhang F M, Zou X Y, Yan P F, et al. Cryst. Growth Des.,2015,15:1249-1258
[24]Zhou Y S, Li X M, Zhang L J, et al. Inorg. Chem., 2014,53(7):3362-3370
[25]Xie W P, Wang N, Long Y, et al. Inorg. Chem. Commun.,2014,40:151-156
[26]Qi Y, Gang X, Qing W, et al. J. Solid State Chem., 2014,215:26-33
[27]Lv Y, Chen Y G, Li X M. Inorg. Chem. Commun., 2014,45:33-35
[28]Liu G X, Xu Y Y, Ren X M, et al. Inorg. Chim. Acta, 2010,363(14):3727-3732
[29]Deng H, Li Y H, Qiu Y C, et al. Inorg. Chem. Commun.,2008,11:1151-1154
[30]Sheldrick G M. SHELXL-97, Program for the Solution and the Refinement of Crystal Structures, University of G觟ttingen,Germany, 1997.
[31]Chi Y X, Niu S Y, Wang Z L, et al. Eur. J. Inorg. Chem.,2008,14:2336-2343
[32]Lin X M, Ying Y, Chen L, et al. Inorg. Chem. Commun.,2009,12(4):316-320
[33]Khlobystov A N, Blake A J, Champness N R, et al. Coord.Chem. Rev., 2001,222(1):155-192
[34]Catalano V J, Malwitz M A. Inorg. Chem., 2003,42:5483-5485
[35]Zhao B, Chen X Y, Wang W Z. Inorg. Chem. Commun., 2005,8(2):178-181
[36]Olson L P, Whitcomb D R, Rajeswaran M, et al. Chem.Mater., 2006,18(6):1667-1674
[37]Yaghi O M, Li H. J. Am. Chem. Soc., 1996,118(1):295-296
[38]Li H R, Zhang H J, Lin J, et al. J. Non-Cryst. Solids, 2000,278:218-222
[39]Yang Y S, Gong M L, Li Y Y, et al. J. Alloys Comp., 1994,207-208:112-114
[40]Brito H F, Malta O L, Felinto M C F C, et al. J. Alloys Comp.,2002,344:293-297
[41]Xu C J, Yang H, Xie F, et al. J. Alloys Compd., 2005,392:96-99
[42]Tang B, Jin L P, Zheng X J, et al. Spectrochim. Acta A,1999,55:1731-1736