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Two new copper(I) iodide-based hybrids, i.e. (Py3P–O–PPy3)(Cu2I4) (1) and (Py3P–O–PPy3)(Cu4I6) (2) (Py = pyrrolidine), have been prepared, in which the tripodal diphosphonium (Py3P–O–PPy3)2+ is in situ generated in the one-pot synthesis. The disordered (Cu4I6)2− tetramers are rare with two sets of tetracuprate centers. Interestingly, 1 exhibits sensitive luminescence mechanochromism, which is ascribed to the disturbed cuprophilic Cu⋯Cu interactions and the crystalline packing adjustment by destroying C–H⋯I hydrogen bonds during mechanical force. In particular, the luminescence thermochromism is unique, whose fluorescence intensity is strengthened with the elevated temperature. This could be due to the S2–S1 internal conversion on the linear P–O–P backbone, which will be bent upon heating. Simultaneous luminescence thermo/mechanochromism can also be monitored in 1. However, no luminescence thermo/mechanochromic performances can be detected in 2, so the luminescence thermo/mechanochromism of 1 could be quenched with DMF. The conclusions in this work might provide a new large-scale synthesis strategy for intelligent responsive luminescent materials. [ABSTRACT FROM AUTHOR]

The development of new‐type memristors with special performance is of great interest. Herein, an inorganic‐organic hybrid crystalline polyoxometalate (POM) with usual dynamic structures is reported and used as active material for fabricating memristor with unique temperature‐regulated resistive switching behaviors. The hybrid POM not only exhibits tunable thermochromic properties, but also thermal‐induced reversible aggregation and disaggregation reactions, leading to reversible structural transformations in SCSC fashion. Further, the memory device using the hybrid POM as active layer exhibits uncommon performance, which can keep resistive switching silent in the low temperature range of 30–150 °C, but show nonvolatile memory behavior in the high temperature range of 150–270 °C. Particularly, the silent and working states at three special temperatures (30, 150 and 270 °C) can be monitored by chromism. The correlation between structure and resistive switching property of the material has been discussed. The work demonstrates that crystalline inorganic‐organic hybrid POMs are promising materials for making memristors with superior performance. [ABSTRACT FROM AUTHOR]

Diphenyliodonium cations were firstly introduced into halobismuthate system to synthesize two new hybrids, i. e. (DPI) 4 (Bi 2 I 10 ) ( 1 ) and (DPI) 4 (Bi 2 Br 10 )·H 2 O ( 2 ) (DPI = diphenyliodonium). Two hybrids are isostructures containing (Bi 2 X 10 ) 4- halobismuthate dimmers and diphenyliodonium cations. Hypervalent I(III)⋯X interactions and C H⋯X (X I, Br) hydrogen bonds stabilize the structures and contribute to the structural extending from 0-D clusters to 2-D layer/1-D chain. The broader absorption spectra and lower energy gap of 1 were led by strong I⋯I interactions. Two compounds display thermochromism behaviors, whose mechanisms were verified by theoretical calculations. [ABSTRACT FROM AUTHOR]