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Systematic structural control of multichromic platinum(II)-diimine complexes ranging from ionic solid to coordination polymer
Title: | Systematic structural control of multichromic platinum(II)-diimine complexes ranging from ionic solid to coordination polymer |
Authors: | Kobayashi, Atsushi Browse this author →KAKEN DB | Hara, Hirofumi Browse this author | Yonemura, Tsubasa Browse this author | Chang, Ho-Chol Browse this author →KAKEN DB | Kato, Masako Browse this author →KAKEN DB |
Issue Date: | 14-Feb-2012 |
Publisher: | Royal Society of Chemistry |
Journal Title: | Dalton Transactions |
Volume: | 41 |
Issue: | 6 |
Start Page: | 1878 |
End Page: | 1888 |
Publisher DOI: | 10.1039/c1dt11155h |
PMID: | 22170569 |
Abstract: | Reactions of a Pt(II)-diimine-based metalloligand Na2[Pt(CN)2(4,4'-dcbpy)] (4,4'-H2dcbpy = 4,4'-dicarboxy-2,2'-bipyridine) with alkaline-earth metal salts Mg(NO3)2・6H2O, CaCl2, SrCl2・6H2O, and BaBr2・2H2O in aqueous solution gave luminescent complexes formulated as [Mg(H2O)5][Pt(CN)2(4,4'-dcbpy)]・4H2O (MgPt-4・9H2O), {[Ca(H2O)3][Pt(CN)2(4,4'-dcbpy)]・3H2O}∞ (CaPt-4・6H2O), {[Sr(H2O)2][Pt(CN)2(4,4'-dcbpy)]・H2O}∞ (SrPt-4・3H2O), and {[Ba(H2O)2][Pt(CN)2(4,4'-dcbpy)]・3H2O}∞ (BaPt-4・5H2O), 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・9H2O, 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(H2O)5][Pt(CN)2(4,4'-dcbpy)]. In contrast, the alkaline-earth metal ion and metalloligand form two-dimensional (CaPt-4・6H2O) and three-dimensional (SrPt-4・3H2O and BaPt-4・5H2O) coordination networks, respectively. All fully hydrated complexes exhibited a strong phosphorescence from the triplet π-π* transition state. Luminescence spectroscopy revealed that MgPt-4・9H2O exhibited interesting multichromic (i.e., thermo-, mechano-, and vapochromic) luminescence, whereas CaPt-4・6H2O 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. |
Rights: | Dalton Trans., 2012, 41, 1878-1888 - Reproduced by permission of The Royal Society of Chemistry (RSC) |
Type: | article (author version) |
URI: | http://hdl.handle.net/2115/50411 |
Appears in Collections: | 理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)
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Submitter: 小林 厚志
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