TY - JOUR
T1 - Extraordinary anisotropic thermal expansion in photosalient crystals
AU - Yadava, Khushboo
AU - Gallo, Gianpiero
AU - Bette, Sebastian
AU - Mulijanto, Caroline Evania
AU - Karothu, Durga Prasad
AU - Park, In Hyeok
AU - Medishetty, Raghavender
AU - Naumov, Pance
AU - Dinnebier, Robert E.
AU - Vittal, Jagadese J.
N1 - © Yadava et al. 2020.
PY - 2020/1/1
Y1 - 2020/1/1
N2 - 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)L 2], where L = 4-styryl pyridine (4spy) (1), 2′-fluoro-4-styryl pyridine (2F-4spy) (2) and 3′-fluoro-4-styryl pyridine (3F-4spy) (3), 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 1, 2 and 3 of 241.8, 233.1 and 285.7 × 10-6 K-1, 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.
AB - 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)L 2], where L = 4-styryl pyridine (4spy) (1), 2′-fluoro-4-styryl pyridine (2F-4spy) (2) and 3′-fluoro-4-styryl pyridine (3F-4spy) (3), 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 1, 2 and 3 of 241.8, 233.1 and 285.7 × 10-6 K-1, 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.
KW - [2+2] cyclo additions
KW - crystal engineering
KW - mechanochemistry
KW - metal complexes
KW - molecular crystals
KW - organic solid-state reactions
KW - photosalient effects
KW - properties of solids
KW - solid-state reactions
KW - thermal expansion
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U2 - 10.1107/S2052252519014581
DO - 10.1107/S2052252519014581
M3 - Article
C2 - 31949907
AN - SCOPUS:85078346702
SN - 2052-2525
VL - 7
SP - 83
EP - 89
JO - IUCrJ
JF - IUCrJ
IS - Pt 1
ER -