Systematic structural control of multichromic platinum(II)-diimine complexes ranging from ionic solid to coordination polymer.
Systematic structural control of multichromic platinum(II)-diimine complexes ranging from ionic solid to coordination polymer.
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DOI：
10.1039/c1dt11155h
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发表时间：
2012-01
影响因子：
4
通讯作者：
A. Kobayashi;Hirofumi Hara;Tsubasa Yonemura;Ho‐Chol Chang;Masako Kato
中科院分区：
文献类型：
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作者：
A. Kobayashi;Hirofumi Hara;Tsubasa Yonemura;Ho‐Chol Chang;Masako Kato
反应的Pt (II) -diimine-based metalloligand Na(2)[葡文(CN)(2)(4, 4’-dcbpy)](4, 4’- H (2) dcbpy = 4, 4’-dicarboxy-2, 2》关于环)与碱土金属盐毫克(没有(3))(2)·6 H (2) O, CaCl (2), SrCl(2)·6 H(2)啊,和BaBr (2) (2) O·2 H在水溶液给发光配合物制定(毫克(H (2) O)(5)][葡文(CN)(2)(4, 4’-dcbpy)]·4 H (2) O (MgPt-4·9 H (2) O), {[Ca (H (2) O)(3)][葡文(CN)(2)(4, 4’-dcbpy)]·3 H (2) O}(∞)(CaPt-4·6 H (2) O), {(Sr (H (2) O)(2)][葡文(CN)(2)(4, 4’-dcbpy)]·H (2) O}(∞)(SrPt-4·3 H (2) O),和{(Ba (H (2) O)(2)][葡文(CN)(2)(4, 4’-dcbpy)]·3 H (2) O}(∞)(BaPt-4·5 H (2) O),分别。所有MPt-4配合物的晶体结构均通过x射线晶体学测定。在这些结构中，碱土金属离子通常与[Pt(CN)(2)(4,4'-dcbpy)]（2-）金属配位体的羧基配位。在MgPt-4·9H(2)O的情况下，Mg（II）离子与五个水分子和一个羧基氧原子结合形成中性络合物分子[Mg(H(2)O)(5)][Pt(CN)(2)(4,4'-dcbpy)]。碱土金属离子和金属配体分别形成二维（cap -4·6H(2)O）和三维(SrPt-4·3H（2)O和bpt -4·5H(2)O）配位网络。所有充分水合的配合物都表现出来自三重态π-π*过渡态的强磷光。发光光谱显示，MgPt-4·9H(2)O表现出有趣的多色（即热致、机械致和气相致）发光，而CaPt-4·6H(2)O仅表现出热致发光。另外两种配合物没有表现出任何变色行为。粉末x射线衍射、热重和红外光谱的综合分析表明，配位网络的维数对结构柔韧性和发光性能都有重要影响；也就是说，MPt-4配合物与较小的碱土金属离子形成的低维柔性配位网络能够在热、机械刺激和蒸汽吸附的诱导下进行结构重排，从而导致观察到的多色行为。
Reactions of a Pt(II)-diimine-based metalloligand Na(2)[Pt(CN)(2)(4,4'-dcbpy)] (4,4'-H(2)dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) with alkaline-earth metal salts Mg(NO(3))(2)·6H(2)O, CaCl(2), SrCl(2)·6H(2)O, and BaBr(2)·2H(2)O in aqueous solution gave luminescent complexes formulated as [Mg(H(2)O)(5)][Pt(CN)(2)(4,4'-dcbpy)]·4H(2)O (MgPt-4·9H(2)O), {[Ca(H(2)O)(3)][Pt(CN)(2)(4,4'-dcbpy)]·3H(2)O}(∞) (CaPt-4·6H(2)O), {[Sr(H(2)O)(2)][Pt(CN)(2)(4,4'-dcbpy)]·H(2)O}(∞) (SrPt-4·3H(2)O), and {[Ba(H(2)O)(2)][Pt(CN)(2)(4,4'-dcbpy)]·3H(2)O}(∞) (BaPt-4·5H(2)O), respectively. The crystal structures of all MPt-4 complexes were determined by X-ray crystallography. In these structures, the alkaline-earth metal ions are commonly coordinated to the carboxyl groups of the [Pt(CN)(2)(4,4'-dcbpy)](2-) metalloligand. In the case of MgPt-4·9H(2)O, the Mg(II) ion is bound by five water molecules and one oxygen atom of a carboxyl group to form a neutral complex molecule [Mg(H(2)O)(5)][Pt(CN)(2)(4,4'-dcbpy)]. In contrast, the alkaline-earth metal ion and metalloligand form two-dimensional (CaPt-4·6H(2)O) and three-dimensional (SrPt-4·3H(2)O and BaPt-4·5H(2)O) coordination networks, respectively. All fully hydrated complexes exhibited a strong phosphorescence from the triplet π-π* transition state. Luminescence spectroscopy revealed that MgPt-4·9H(2)O exhibited interesting multichromic (i.e., thermo-, mechano-, and vapochromic) luminescence, whereas CaPt-4·6H(2)O showed only thermochromic luminescence. The other two complexes did not exhibit any chromic behaviour. Combination analysis of powder X-ray diffraction, thermogravimetry, and IR spectroscopy suggests that the dimensionality of the coordination network contributes considerably to both the structural flexibility and luminescence properties; that is, the low-dimensional flexible coordination network formed in MPt-4 complexes with smaller alkaline-earth metal ions enables a structural rearrangement induced by thermal and mechanical stimuli and vapour adsorption, resulting in the observed multichromic behaviour.