Yadava Khushboo, Gallo Gianpiero, Bette Sebastian, Mulijanto Caroline Evania, Karothu Durga Prasad, Park In-Hyeok, Medishetty Raghavender, Naumov Panče, Dinnebier Robert E, Vittal Jagadese J
Department of Chemistry, National University of Singapore, S8-05-03, 3 Science Drive 3, 117543, Singapore.
Max Planck Institute for Solid State Research, Heisenbergstrasse 1, D70569 Stuttgart Germany.
IUCrJ. 2020 Jan 1;7(Pt 1):83-89. doi: 10.1107/S2052252519014581.
Although a plethora of metal complexes have been characterized, those having multifunctional properties are very rare. This article reports three isotypical complexes, namely [Cu(benzoate) ], where = 4-styryl-pyridine (4spy) (), 2'-fluoro-4-styryl-pyridine (2F-4spy) () and 3'-fluoro-4-styryl-pyridine (3F-4spy) (), which show photosalient behavior (photoinduced crystal mobility) while they undergo [2+2] cyclo-addition. These crystals also exhibit anisotropic thermal expansion when heated from room temperature to 200°C. The overall thermal expansion of the crystals is impressive, with the largest volumetric thermal expansion coefficients for , and of 241.8, 233.1 and 285.7 × 10 K, respectively, values that are comparable to only a handful of other reported materials known to undergo colossal thermal expansion. As a result of the expansion, their single crystals occasionally move by rolling. Altogether, these materials exhibit unusual and hitherto untapped solid-state properties.
尽管已经对大量金属配合物进行了表征，但具有多功能特性的金属配合物却非常罕见。本文报道了三种同型配合物，即[Cu(苯甲酸酯)]，其中 = 4-苯乙烯基吡啶(4spy) ()、2'-氟-4-苯乙烯基吡啶(2F-4spy) ()和3'-氟-4-苯乙烯基吡啶(3F-4spy) ()，它们在进行[2+2]环加成时表现出光致跃变行为(光诱导晶体迁移)。当从室温加热到200°C时，这些晶体还表现出各向异性热膨胀。晶体的整体热膨胀令人印象深刻，其中 、 和 的最大体积热膨胀系数分别为241.8、233.1和285.7×10 K，这些值仅与少数其他已知经历巨大热膨胀的报道材料相当。由于膨胀，它们的单晶偶尔会通过滚动而移动。总之，这些材料表现出不寻常且迄今尚未开发的固态特性。
