1,3-二(4-吡啶基)-丙烷与邻苯二甲酸构筑的过渡金属配合物的合成、结构和荧光性质

doi:10.7503/cjcu20160958

摘要/Abstract

摘要：

以1,3-二(4-吡啶基)-丙烷(bpp)和邻苯二甲酸(1,2-H₂bdc)为配体, 通过水热法合成了过渡金属配合物M₂(1,2-bdc)₂(bpp)₂·2H₂O[M=Co(1), Ni(2)]和Cd(1,2-bdc)(bpp)·H₂O(3). 配合物1和2属单斜晶系P2₁空间群, 具有相似的三维骨架结构. 配合物中存在2种配位环境相似的金属中心, 每个金属中心采取六配位的畸变八面体构型, 与来自2个1,2-bdc配体的3个氧原子和2个bpp配体的2个氮原子以及1个水分子配位. 1,2-bdc配体采取单齿/双齿螯合的配位模式将金属离子连接成M1-(1,2-bdc)-M2右手螺旋链. bpp配体采取Trans-Gauche(TG)构型, 连接相邻的金属离子形成M1-(bpp)-M1链和M2-(bpp)-M2链. 这3种链交织在一起构筑成具有{6⁵. 8}拓扑的三维结构. 配合物3属单斜晶系P2₁/c空间群, 具有单节点的双层二维结构. Cd(Ⅱ)离子采取七配位的畸变五角双锥体构型, 与来自2个1,2-bdc配体的4个氧原子, 2个bpp配体的2个氮原子和1个水分子配位. 1,2-bdc配体采取双齿螯合/双齿螯合的配位模式将Cd(Ⅱ)离子连接成Cd-(1,2-bdc)-Cd链. bpp配体采取TG构型, 连接相邻的Cd(Ⅱ)离子, 形成Cd-(bpp)-Cd链. 这2种链通过共享Cd(Ⅱ)离子交错排列构筑成二维结构. 配合物3显示出强的荧光, 最大发射位于408 nm处, 对应于配体的π^*-π跃迁. 不同有机小分子对配合物3的荧光强度有不同程度的影响, 苯胺对其有显著的猝灭作用, 基于荧光猝灭机理, 配合物3可用于选择性检测苯胺分子.

关键词: 过渡金属配合物, 1, 3-二(4-吡啶基)-丙烷, 邻苯二甲酸, 晶体结构, 荧光

Abstract:

Taking 1,3-di(4-pyridyl)-propane(bpp) and 1,2-benzenedicarboxylic acid(1,2-H₂bdc) as ligands, three new transition metal complexes, M₂(1,2-bdc)₂(bpp)₂·2H₂O[M(Ⅱ)=Co(1), Ni(2)] and Cd(1,2-bdc)(bpp)·H₂O(3), were obtained. Complexes 1 and 2 crystallize in monoclinic crystal system with space group P2₁ and show 3D structures with {6⁵·8} topology. There are two M(Ⅱ) centers with the similar coordination environments in complexes 1 and 2. Each M(Ⅱ) center is six-coordinated to three oxygen atoms from two 1,2-bdc ligands, two nitrogen atoms from bpp ligands and one water molecule in a distorted octahedral arrangement. The 1,2-bdc ligand adopts monodentate bridging/bidentate chelating mode to link two metal centers to form M1-(bpp)-M1 right-handed-helical chain. The bpp ligand adopts Trans-Gauche(TG) conformation and connects adjacent M(Ⅱ) centers to form M1-(bpp)-M1 and M2-(bpp)-M2 chains. These three kinds of chains are woven together to form a 3D framework. Complex 3 crystallizes in monoclinic crystal system with space group P2₁/c and shows a 2D structure. The Cd(Ⅱ) is in distorted pentagonal bipyramidal polyhedron with four oxygen atoms of two 1,2-bdc ligands, two nitrogen atoms of bpp ligand and one water molecule. The 1,2-bdc ligand adopts bi(bidentate chelating) mode to link Cd(Ⅱ) centers to form Cd-(1,2-bdc)-Cd chain. The bpp ligand adopts TG conformation and connects Cd(Ⅱ) centers to form Cd-(bpp)-Cd chain. The two kinds of chains with shared Cd(Ⅱ) are alternately arranged to form a 2D structure. Complex 3 shows strong ligand-based fluorescence with maximum emission at 408 nm, which is attributed to π^*-π transition of the ligands. Different organic small molecules have different effects on the fluorescence intensity of complex 3, and aniline has a significant quenching effect, thus complex 3 can be used for the selective detection of aniline through fluorescence quenching mechanism.

Key words: Transition metal complex, 1, 3-Di(4-pyridyl)-propane, 1, 2-Benzenedicarboxylic acid, Crystal structure, Fluorescence

王秋爽, 郑晓丽, 屈相龙, 李睿, 李夏. 1,3-二(4-吡啶基)-丙烷与邻苯二甲酸构筑的过渡金属配合物的合成、结构和荧光性质[J]. 高等学校化学学报, 2017, 38(7): 1125-1133.

WANG Qiushuang, ZHENG Xiaoli, QU Xianglong, LI Rui, LI Xia. Synthesis, Structure and Luminescence Property of Transition Metal Complexes with 1,3-Di(4-pyridyl)-propane and 1,2-Benzenedicarboxylic Acid^†[J]. Chemical Journal of Chinese Universities, 2017, 38(7): 1125-1133.

图/表 11

参考文献 41

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Complex	1	2	3
Empirical formula	C₄₂H₄₀N₄O₁₀Co₂	C₄₂H₄₀N₄O₁₀Ni₂	C₂₁H₂₀N₂O₅Cd
Formula weight	878.64	878.20	492.79
Temperature/K	120(2)	120(2)	120(2)
Crystal system	Monoclinic	Monoclinic	Monoclinic
Space group	P2₁	P2₁	P2₁/c
a/nm	1.16755(2)	1.1609(3)	1.04635(8)
b/nm	1.4003(2)	1.3986(3)	1.01448(8)
c/nm	1.18421(2)	1.1847(3)	1.87662(1)
β/(°)	96.298(2)	96.632(3)	109.661(3)
V/nm³	1.9244(5)	1.9107(7)	1.8759(2)
Z	2	2	4
D_c/(g·cm^-3)	1.516	1.526	1.745
Absorption coefficient/mm^-1	0.928	1.052	1.202
F(000)	908	912	992
Crystal size/mm	0.38×0.34×0.30	0.42×0.15×0.10	0.15×0.10×0.07
θ range for data collection/(°)	1.730—25.249	2.26—25.25	2.07—27.63
Limiting indices	-14≤h≤10, -16≤k≤16,	-13≤h≤13, -16≤k≤8,	-13≤h≤12, -13≤k≤13,
	-12≤l≤14	-14≤l≤13	-24≤l≤20
Reflections collected	9762	9035	10882
R_int	0.0220	0.0322	0.0311
Data/restraints/parameters	6637/7/535	4556/31/554	4307/39/280
Goodness-of-fit on F²	1.028	1.062	1.025
Final R indices[I>2σ(I)]	R₁=0.0373, wR₂=0.0887	R₁=0.0501, wR₂= 0.1463	R₁=0.0284, wR₂= 0.0604
R indices(all data)	R₁=0.0405, wR₂=0.0907	R₁=0.0525, wR₂=0.1478	R₁=0.0358, wR₂= 0.0636
CCDC No.	1522654	1522656	1522655

Complex	1	2	3
Empirical formula	C₄₂H₄₀N₄O₁₀Co₂	C₄₂H₄₀N₄O₁₀Ni₂	C₂₁H₂₀N₂O₅Cd
Formula weight	878.64	878.20	492.79
Temperature/K	120(2)	120(2)	120(2)
Crystal system	Monoclinic	Monoclinic	Monoclinic
Space group	P2₁	P2₁	P2₁/c
a/nm	1.16755(2)	1.1609(3)	1.04635(8)
b/nm	1.4003(2)	1.3986(3)	1.01448(8)
c/nm	1.18421(2)	1.1847(3)	1.87662(1)
β/(°)	96.298(2)	96.632(3)	109.661(3)
V/nm³	1.9244(5)	1.9107(7)	1.8759(2)
Z	2	2	4
D_c/(g·cm^-3)	1.516	1.526	1.745
Absorption coefficient/mm^-1	0.928	1.052	1.202
F(000)	908	912	992
Crystal size/mm	0.38×0.34×0.30	0.42×0.15×0.10	0.15×0.10×0.07
θ range for data collection/(°)	1.730—25.249	2.26—25.25	2.07—27.63
Limiting indices	-14≤h≤10, -16≤k≤16,	-13≤h≤13, -16≤k≤8,	-13≤h≤12, -13≤k≤13,
	-12≤l≤14	-14≤l≤13	-24≤l≤20
Reflections collected	9762	9035	10882
R_int	0.0220	0.0322	0.0311
Data/restraints/parameters	6637/7/535	4556/31/554	4307/39/280
Goodness-of-fit on F²	1.028	1.062	1.025
Final R indices[I>2σ(I)]	R₁=0.0373, wR₂=0.0887	R₁=0.0501, wR₂= 0.1463	R₁=0.0284, wR₂= 0.0604
R indices(all data)	R₁=0.0405, wR₂=0.0907	R₁=0.0525, wR₂=0.1478	R₁=0.0358, wR₂= 0.0636
CCDC No.	1522654	1522656	1522655

Co1—O6	0.2020(4)	Co1—O1	0.2153(4)	Co2—O8	0.2102(4)
Co1—N2A	0.2105(5)	Co1—O2	0.2212(4)	Co2—N3	0.2112(5)
Co1—N1	0.2110(5)	Co2—O4B	0.1987(4)	Co2—O10	0.2185(4)
Co1—O5	0.2152(4)	Co2—N4C	0.2095(5)	Co2—O9	0.2237(4)
O6—Co1—N2A	100.21(18)	O6—Co1—O2	94.71(16)	O8—Co2—N3	94.64(16)
O6—Co1—N1	92.04(17)	N2A—Co1—O2	164.30(16)	O4B—Co2—O10	89.72(16)
N2A—Co1—N1	92.14(18)	N1—Co1—O2	92.18(17)	N4C—Co2—O10	84.56(17)
O6—Co1—O5	90.58(16)	O5—Co1—O2	89.73(16)	O8—Co2—O10	85.50(15)
N2A—Co1—O5	85.30(17)	O1—Co1—O2	60.59(14)	N3—Co2—O10	179.62(18)
N1—Co1—O5	176.63(18)	O4B—Co2—N4C	100.76(18)	O4B—Co2—O9	97.62(15)
O6—Co1—O1	154.37(16)	O4B—Co2—O8	158.35(16)	N4C—Co2—O9	159.14(16)
N2A—Co1—O1	103.95(17)	N4C—Co2—O8	99.79(17)	O8—Co2—O9	61.00(14)
N1—Co1—O1	95.45(17)	O4B—Co2—N3	90.28(17)	N3—Co2—O9	94.61(16)
O5—Co1—O1	83.07(15)	N4C—Co2—N3	95.07(18)	O10—Co2—O9	85.76(15)

Co1—O6	0.2020(4)	Co1—O1	0.2153(4)	Co2—O8	0.2102(4)
Co1—N2A	0.2105(5)	Co1—O2	0.2212(4)	Co2—N3	0.2112(5)
Co1—N1	0.2110(5)	Co2—O4B	0.1987(4)	Co2—O10	0.2185(4)
Co1—O5	0.2152(4)	Co2—N4C	0.2095(5)	Co2—O9	0.2237(4)
O6—Co1—N2A	100.21(18)	O6—Co1—O2	94.71(16)	O8—Co2—N3	94.64(16)
O6—Co1—N1	92.04(17)	N2A—Co1—O2	164.30(16)	O4B—Co2—O10	89.72(16)
N2A—Co1—N1	92.14(18)	N1—Co1—O2	92.18(17)	N4C—Co2—O10	84.56(17)
O6—Co1—O5	90.58(16)	O5—Co1—O2	89.73(16)	O8—Co2—O10	85.50(15)
N2A—Co1—O5	85.30(17)	O1—Co1—O2	60.59(14)	N3—Co2—O10	179.62(18)
N1—Co1—O5	176.63(18)	O4B—Co2—N4C	100.76(18)	O4B—Co2—O9	97.62(15)
O6—Co1—O1	154.37(16)	O4B—Co2—O8	158.35(16)	N4C—Co2—O9	159.14(16)
N2A—Co1—O1	103.95(17)	N4C—Co2—O8	99.79(17)	O8—Co2—O9	61.00(14)
N1—Co1—O1	95.45(17)	O4B—Co2—N3	90.28(17)	N3—Co2—O9	94.61(16)
O5—Co1—O1	83.07(15)	N4C—Co2—N3	95.07(18)	O10—Co2—O9	85.76(15)

Ni1—O6	0.2009(6)	Ni1—O1	0.2128(5)	Ni2—N3	0.2075(6)
Ni1—N2A	0.2053(7)	Ni1—O2	0.2145(5)	Ni2—O8	0.2080(5)
Ni1—N1	0.2066(6)	Ni2—O4B	0.1985(5)	Ni2—O10	0.2117(5)
Ni1—O5	0.2108(6)	Ni2—N4C	0.2048(7)	Ni2—O9	0.2178(5)
O6—Ni1—N2A	98.3(2)	O6—Ni1—O2	96.6(2)	N3—Ni2—O8	93.5(2)
O6—Ni1—N1	91.6(2)	N2A—Ni1—O2	164.2(2)	O4B—Ni2—O10	89.8(2)
N2A—Ni1—N1	91.5(3)	N1—Ni1—O2	93.2(2)	N4C—Ni2—O10	85.0(2)
O6—Ni1—O5	90.5(2)	O5—Ni1—O2	88.8(2)	N3—Ni2—O10	179.6(3)
N2A—Ni1—O5	85.9(2)	O1—Ni1—O2	62.2(2)	O8—Ni2—O10	86.6(2)
N1—Ni1—O5	176.9(3)	O4B—Ni2—N4C	97.6(2)	O4B—Ni2—O9	100.1(2)
O6—Ni1—O1	158.1(2)	O4B—Ni2—N3	90.3(2)	N4C—Ni2—O9	160.3(2)
N2A—Ni1—O1	102.4(2)	N4C—Ni2—N3	94.6(3)	N3—Ni2—O9	94.0(2)
N1—Ni1—O1	94.8(2)	O4B—Ni2—O8	162.1(2)	O8—Ni2—O9	62.2(2)
O5—Ni1—O1	84.0(2)	N4C—Ni2—O8	99.5(2)	O10—Ni2—O9	86.4(2)