Syntheses, structures, photoluminescence, and theoretical studies of d(10) metal complexes of 2,2'-dihydroxy-[1,1']binaphthalenyl-3,3'-dicarboxylate.
Syntheses, structures, photoluminescence, and theoretical studies of d(10) metal complexes of 2,2'-dihydroxy-[1,1']binaphthalenyl-3,3'-dicarboxylate.
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DOI：
10.1021/ic034847i
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发表时间：
2004-01
影响因子：
4.6
通讯作者：
Shao-Liang Zheng;Jin-Hua Yang;X. Yu;Xiao‐Ming Chen;W. Wong
中科院分区：
文献类型：
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作者：
Shao-Liang Zheng;Jin-Hua Yang;X. Yu;Xiao‐Ming Chen;W. Wong
自由溶剂化配体H（2）bna·CH（3）OH·H（2）O（1）及其二聚配合物[Cd（2）（bna）（2）（H（2）O）（6）]（2）（BNA = 2，2 ′-二羟基-[1，1 ′]-联萘-3，3 ′-二羧酸酯），而两种新的D（10）金属-羟基簇基配位聚合物，通过水热法合成了[Cd（8）（OH）（4）（H（2）O）（10）（bna）（6）]·17 H（2）O（3）和[Hpy]（2）[Zn（4）（OH）（2）（H（2）O）（2）（bna）（4）]·2 H（2）O·2CH（3）CN（4）.所有的化合物已通过X射线晶体学和光致发光测量进行了表征。化合物1由三维氢键超分子阵列组成，化合物2表现出二聚体分子，其特征在于由两个Cd（II）原子和两个bna配体各自在角处组织的正方形基序，和3含有前所未有的[Cd（8）（micro（3）-OH）（2）]（微OH）（2）（micro-H（2）O）（2）]（12+）八核金属冠核，其通过bna互连以提供二维结构，而4的特征层为蝶形[Zn（4）（micro（3）-OH）（2）]（6+）簇合物。所有的配合物显示在蓝色/绿色范围内的光致发光特性。光致发光的表现形式，探测的配合物和假设的多核配合物上进行的分子轨道计算，是由于配体到金属的电荷转移机制。除了提出了一种新的方法来研究的光致发光性能的金属簇基配位聚合物通过使用简单的模型化合物，该研究还揭示了主导作用的结构的配体的d（10）金属羟基（或氧）簇和簇的存在显着增加的发光寿命。
The free solvated ligand, H(2)bna.CH(3)OH.H(2)O (1), and its dimeric complex, [Cd(2)(bna)(2)(H(2)O)(6)] (2) (bna = 2,2'-dihydroxy-[1,1']-binaphthalene-3,3'-dicarboxylate), were obtained by evaporation of the solutions, while two new d(10) metal-hydroxy cluster-based coordination polymers, namely [Cd(8)(OH)(4)(H(2)O)(10)(bna)(6)].17H(2)O (3) and [Hpy](2)[Zn(4)(OH)(2)(H(2)O)(2)(bna)(4)].2H(2)O.2CH(3)CN (4), were obtained by a hydrothermal route. All the compounds have been characterized by X-ray crystallography and photoluminescence measurements. Compound 1 consists of a three-dimensional, hydrogen-bonded supramolecular array, 2 exhibits a dimeric molecule featuring a square motif organized by two Cd(II) atoms and two bna ligands each at the corner, and 3 contains unprecedented [Cd(8)(micro(3)-OH)(2)(micro-OH)(2)(micro-H(2)O)(2)](12+) octanuclear metallacrown cores which are interlinked through bna to afford a two-dimensional structure, while 4 features layers with butterfly-shaped [Zn(4)(micro(3)-OH)(2)](6+) clusters. All the complexes display photoluminescent properties in the blue/green range. The manifestation of photoluminescence, as probed by molecular orbital calculations performed on the complexes and also on hypothetical multinuclear complexes, is attributed to a ligand-to-metal charge-transfer mechanism. In addition to presenting a new approach for the study of the photoluminescent properties of metal-cluster-based coordination polymers by using simple model compounds, the study also reveals the dominant role of the structure of the ligand over that of the d(10) metal-hydroxy (or oxy) cluster and the presence of the cluster significantly increasing the emission lifetime.