两个基于氢键构筑的超分子镁配合物的合成、 晶体结构及荧光性质

doi:10.7503/cjcu20160908

摘要/Abstract

摘要：

以5,6-苯并咪唑二酸(H₃bidc)为有机配体, 在水热条件下通过控制反应温度得到了2个镁配合物[Mg(Hbidc)(H₂O)₄](1) 和 [Mg(Hbidc)(H₂O)₅]·4H₂O(2). 通过单晶及粉末X 射线衍射、红外光谱、元素分析和热重分析对配合物进行了表征. 结果表明, 配合物1和2均为单核分子, 分别以不同的堆积方式通过氢键构筑成三维超分子结构. 值得注意的是, 配合物2的结构中捕获了由氢键连接的环状四聚体水簇(H₂O)₄. 配合物1和2的电荷布居分析结果与晶体结构的讨论一致. 此外, 固体荧光分析表明, 配合物1和2在室温下具有较强的蓝光发射.

关键词: Mg(Ⅱ)配合物, 反应温度, 氢键, 荧光寿命

Abstract:

Two structurally diverse magnesium centered complexes with formula [Mg(Hbidc)(H₂O)₄](1) and [Mg(Hbidc)(H₂O)₅]·4H₂O(2), constructed from multidentate ligand 1H-benzimidazole-5,6-dicarboxylic acid(H₃bidc), were synthesized under hydrothermal conditions with identical reactants at different temperatures. The complexes were characterized by Fourier transform infrared(FTIR) spectroscopy, elemental analysis, thermogravimetric analysis(TGA), and powder and single-crystal X-ray diffraction(XRD) analyses. Complexes 1 and 2 both display neutral mononuclear structures, and their distinct crystal packing patterns are driven by strong intra- or inter-molecular hydrogen bonds. Interestingly, unprecedented hydrogen-bonded cyclic tetrameric water clusters(H₂O)₄ are observed in complex 2. In addition, luminescent studies show that the title compounds exhibit intense blue fluorescence emissions at room temperature in the solid state.

Key words: Magnesium(Ⅱ) complex, Reaction temperature, Hydrogen bond, Fluorescence lifetime

中图分类号:

O614.22

孙佳音, 卢可, 刘广志, 刘璐, 潘文蓉, 张思静, 秦伟, 吴根华. 两个基于氢键构筑的超分子镁配合物的合成、晶体结构及荧光性质[J]. 高等学校化学学报, 2017, 38(5): 729-737.

SUN Jiayin, LU Ke, LIU Guangzhi, LIU Lu, PAN Wenrong, ZHANG Sijing, QIN Wei, WU Genhua. Syntheses, Crystal Structures and Luminescent Properties of Two Magnesium(Ⅱ) Supramolecular Architectures Based on Hydrogen Bonds^†[J]. Chemical Journal of Chinese Universities, 2017, 38(5): 729-737.

图/表 12

Table 1 Crystal data and structure refinement parameters for complexes 1 and 2

Compound	1	2	γ/(°)	105.4980(10)	78.03(3)
Formula	C₉H₁₂MgN₂O₈	C₉H₂₂MgN₂O₁₃	V/nm³	0.57579(7)	0.8534(3)
Formula weight	300.52	390.60	Z	2	2
Crystal system	Triclinic	Triclinic	D_c/(g·cm³)	1.733	1.520
Space group	P $1 ˉ$	P $1 ˉ$	μ/mm^-1	0.200	0.174
a/nm	0.68005(5)	0.68302(14)	F(000)	312.0	412
b/nm	0.72370(5)	1.1021(2)	R_int	0.0165	0.0401
c/nm	1.22063(9)	1.1713(2)	GOF	1.068	1.050
α/(°)	92.5300(10)	87.22(3)	R₁, wR₂[I>2σ(I)]	0.0363/0.0939	0.0501/0.1255
β(°)	94.4880(10)	81.70(3)	R₁, wR₂(all data)	0.0449/0.0994	0.0649/0.1357

Table 1 Crystal data and structure refinement parameters for complexes 1 and 2

Compound	1	2	γ/(°)	105.4980(10)	78.03(3)
Formula	C₉H₁₂MgN₂O₈	C₉H₂₂MgN₂O₁₃	V/nm³	0.57579(7)	0.8534(3)
Formula weight	300.52	390.60	Z	2	2
Crystal system	Triclinic	Triclinic	D_c/(g·cm³)	1.733	1.520
Space group	P $1 ˉ$	P $1 ˉ$	μ/mm^-1	0.200	0.174
a/nm	0.68005(5)	0.68302(14)	F(000)	312.0	412
b/nm	0.72370(5)	1.1021(2)	R_int	0.0165	0.0401
c/nm	1.22063(9)	1.1713(2)	GOF	1.068	1.050
α/(°)	92.5300(10)	87.22(3)	R₁, wR₂[I>2σ(I)]	0.0363/0.0939	0.0501/0.1255
β(°)	94.4880(10)	81.70(3)	R₁, wR₂(all data)	0.0449/0.0994	0.0649/0.1357

Fig.1 View of the asymmetric unit(A), 1D ladder chain formed by dimeric [Mg(Hbidc)(H2O)4]2 ring along a axis(B), 3D supramolecular framework(C) and topological representation of the 3D H-bonded network displaying a diamondoid network(D) of complex 1The dashed lines represent the H-bonds.

Table 2 Bond lengths and bond angles of hydrogen bonds for complex 1*

D—H…A	d(D—H)/nm	d(H…A)/nm	d(D…A)/nm	∠(DHA)/(°)
O6—H6'…O8#1	0.078(4)	0.234(4)	0.2952(3)	135(4)
O8—H8'…O4#2	0.083(3)	0.189(3)	0.2713(2)	172(3)
O7—H7'…O3#3	0.086(4)	0.195(4)	0.2759(2)	157(3)
O6—H6…O3#4	0.082(3)	0.245(3)	0.2916(2)	118(3)
O6—H6…O1#3	0.082(3)	0.216(3)	0.2864(3)	143(3)
O5—H5'…O1#3	0.085(4)	0.197(3)	0.2767(2)	154(3)
O7—H7…O3#2	0.090(3)	0.184(3)	0.2733(2)	172(3)
O8—H8…O2#1	0.087(4)	0.188(4)	0.2722(2)	164(3)
O5—H5…N2#5	0.088(4)	0.187(4)	0.2729(2)	167(3)
N1—H1…O5#6	0.079(3)	0.214(3)	0.2919(3)	166(3)

Fig.2 View of the asymmetric unit(A), 3D supramolecular framework along the bc plane(B), 2D supramolecular plane trapped tetramer water cyclic (H2O)4(C) and topological representation of the 3D H-bonded network displaying an sqp network(D) of complex 2The dashedlines represent the H-bonds.

Fig.3 View of the water tape in complex 2 containing the uuud configuration of cyclic tetramer water(H2O)4The dashed lines represent the H-bonds.

Table 3 Bond lengths and bond angles of hydrogen bonds for complex 2*

D—H…A	d(D—H)/nm	d(H…A)/nm	d(D…A)/nm	∠(DHA)/(°)
O2—H17…O12#1	0.090(4)	0.179(5)	0.2683(3)	176(4)
O4—H16…O2	0.086(4)	0.205(4)	0.2907(3)	169(3)
O4—H15…O9#2	0.085(3)	0.202(3)	0.2807(3)	153(3)
N2—H2…O3#3	0.086	0.196	0.2811(3)	170.9
O9—H12…O10#4	0.073(3)	0.193(3)	0.2661(3)	173(3)
O5—H8…O12#5	0.075(4)	0.205(4)	0.2756(3)	158(4)
O6—H5…O13#6	0.077(4)	0.200(4)	0.2776(3)	180(4)
O7—H9…O12#5	0.086(4)	0.203(4)	0.2830(3)	154(3)
O5—H11…O13#7	0.088(4)	0.188(4)	0.2753(3)	173(3)
O6—H6…O2	0.080(4)	0.202(4)	0.2790(3)	162(3)
O8—H13…O11#4	0.087(4)	0.177(4)	0.2637(3)	172(4)
O8—H3…O4	0.071(4)	0.209(4)	0.2805(3)	177(4)
O9—H14…O1#8	0.093(5)	0.175(5)	0.2678(3)	171(4)
O7—H10…O4#9	0.088(4)	0.197(4)	0.2841(3)	175(3)
O3—H21…O10#5	0.088(4)	0.187(4)	0.2738(3)	168(3)
O3—H22…O11#1	0.089(4)	0.184(4)	0.2716(3)	170(4)
O1—H19…O3#10	0.085(5)	0.201(5)	0.2824(4)	159(4)
O1—H20…O8	0.080(5)	0.215(5)	0.2923(3)	162(4)

Fig.4 Experimental(a) and simulated(b) PXRD patterns of complexes 1(A) and 2(B)

Fig.5 TGA curves of complexes 1(a) and 2(b) under N2 atmosphere

Fig.6 Solid-state emission spectra(A) and CIE color coordinates(B) of complexes 1(a) and 2(b)

Fig.7 Decay curves of complexes 1(A) and 2(B)

Table 4 Mulliken atomic charges of compound 1 and H3bidc ligand

Atom	Charge		Atom	Charge		Atom	Charge		Atom	Charge
Atom	1		H₃bidc		1	Atom	H₃bidc	1	H₃bidc	1	H₃bidc
Mg1	1.491		O4	-0.732	-0.578	C7	-0.026	0.026	H5'	0.539
O5	-1.077		N1	-0.575	-0.541	C4	0.079	0.166	H6	0.541
O6	-1.018		N2	-0.515	-0.405	C8	0.568	0.539	H6'	0.519
O7	-1.049		C1	-0.058	0.026	C9	0.604	0.529	H7	0.508
O8	-1.080		C2	-0.349	-0.191	H2	0.283	0.193	H7'	0.525
O1	-0.627	-0.519	C3	0.234	0.255	H3	0.309		H8	0.535
O2	-0.737	-0.553	C5	0.204	0.214	H1	0.523	0.352	H8'	0.544
O3	-0.662	-0.451	C6	-0.331	-0.221	H5	0.538		H4	0.290	0.191

Table 5 Mulliken atomic charges of compound 2 and H3bidc ligand

Atom	Charge		Atom	Charge		Atom	Charge		Atom	Charge
Atom	2		H₃bidc		2	Atom	H₃bidc	2	H₃bidc	2	H₃bidc
Mg	1.510		O12	-0.751	-0.578	C9	0.572	0.539	H12	0.522
O1	-0.997		O13	-0.656	-0.553	H1	0.289	0.191	H13	0.520
O2	-0.989		N1	-0.587	-0.405	H4	0.376	0.193	H14	0.538
O3	-1.029		N2	-0.551	-0.541	H7	0.274	0.163	H16	0.518
O4	-1.023		C1	0.077	0.166	H2	0.507	0.352	H18	0.466
O5	-1.048		C2	0.230	0.214	H3	0.520		H19	0.503
O6	-1.030		C3	0.230	0.255	H5	0.525		H20	0.511
O7	-1.039		C4	-0.354	-0.191	H6	0.529		H21	0.521
O8	-1.067		C5	-0.040	0.026	H8	0.511		H22	0.516
O9	-1.085		C6	-0.044	0.026	H9	0.521
O10	-0.669	-0.519	C7	-0.342	-0.221	H10	0.521
O11	-0.676	-0.451	C8	0.589	0.529	H11	0.521

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