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000642746 0247_ $$2doi$$a10.26434/chemrxiv-2025-dl8vn-v2
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000642746 245__ $$aIn-situ Diffraction Crystallization Study of a porous Ti(IV) oxo-cluster carboxylate MOF and its Water-Induced Ti(III) Formate
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000642746 520__ $$aThe in-situ crystallization kinetics of the highly porous Ti(IV)12 oxo-cluster based metal-organic framework (MOF) MIP-177(Ti)-LT (MIP: Materials from Institute of porous solids of Paris, LT: Low Temperature) were studied by synchrotron time-resolved powder X-ray diffraction. When dry formic acid (FA) was used as solvent the crystallization does follow the Johnson-Mehl-Avrami-Kolmogorov kinetics with an energy barrier of 74 kJ·mol-1 without any observed intermediate crystalline phases. However, when small quantities of water (≥ 2.5 vol%) were introduced in the reaction solution, it led to the formation of the novel clathrate Ti(HCOO)3·¾CO2·¼H2O, a microporous MOF belonging to the ReO3 net-like CO2 clathrates in analogy to the previously described M(III)-formates (M = Al, Mn, Fe, Ga, In). Although the formation mechanism in the presence of water remains unclear, one possible explanation is that MIP-177(Ti⁴⁺)-LT decomposes formic acid under solvothermal conditions, resulting in the production of CO₂ and H₂, which may promote the crystallization of Ti³⁺-formate clathrate.
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000642746 7001_ $$aChen, Bingbing$$b1
000642746 7001_ $$0P:(DE-H253)PIP1102601$$aMelillo, Arianna$$b2
000642746 7001_ $$00000-0003-2025-4115$$aWahiduzzaman, Mohammad$$b3
000642746 7001_ $$0P:(DE-H253)PIP1085741$$aKhadiev, Azat$$b4
000642746 7001_ $$0P:(DE-H253)PIP1001864$$aNovikov, Dmitri$$b5$$udesy
000642746 7001_ $$0P:(DE-H253)PIP1098547$$aAchenbach, Bastian$$b6
000642746 7001_ $$0P:(DE-H253)PIP1032512$$aRuser, Niklas$$b7
000642746 7001_ $$0P:(DE-H253)PIP1087992$$aGosch, Jonas$$b8
000642746 7001_ $$0P:(DE-H253)PIP1007798$$aStock, Norbert$$b9
000642746 7001_ $$aMaurin, Guillaume$$b10
000642746 7001_ $$0P:(DE-H253)PIP1096258$$aMouchaham, Georges$$b11
000642746 7001_ $$0P:(DE-H253)PIP1007877$$aSerre, Christian$$b12
000642746 773__ $$a10.26434/chemrxiv-2025-dl8vn-v2
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