Unravelling the Growth of Supramolecular Metal鈥揙rganic Frameworks Based on Metal-Nucleobase Entities

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• 作者：Jintha Thomas-Gipson ; Rub茅n P茅rez-Aguirre ; Garikoitz Beobide ; Oscar Castillo ; Antonio Luque ; Sonia P茅rez-Y谩帽ez ; Pascual Rom谩n
• 刊名：Crystal Growth & Design
• 出版年：2015
• 出版时间：February 4, 2015
• 年：2015
• 卷：15
• 期：2
• 页码：975-983
• 全文大小：534K
• ISSN：1528-7505

文摘

The present work provides the basis to obtain three-dimensional (3D) extended porous supramolecular assemblies named supramolecular metal鈥搊rganic frameworks (SMOFs). This goal can be achieved by considering three key factors: (i) the use of rigid building units, (ii) the establishment of predictable and rigid synthons between the building units, and (iii) the non-coplanarity of functional groups involved in the predictable synthons. Throughout this report we demonstrate the suitability of this synthetic strategy supported by six new SMOFs based on metal-nucleobase entities which fulfill the stated requirements: [Co(ThioG)₃] (SMOF-4; ThioG = thioguaninato), [Co(Hade)₂X₂] (SMOF-5, SMOF-6; Hade = adenine and X = Cl^{鈥?/sup>, Br鈥?/sup>), [Cu₈(渭₃-OH)₄(渭₄-OH)₄(ade)₄(渭-ade)₄(渭-Hade)₂] (SMOF-7; ade = adeninato), [Cu₄(渭₃-ade)₄(渭-ade)₂(pentylNH₂)₂(CH₃OH)₂(CO₃)₂(H₂O)₂] (SMOF-8; pentylNH₂ = 1-pentylamine), and [Cu₂(渭-ade)₂(ade)(渭-OH)(H₂O)(CH₃OH)]_n (SMOF-9). SMOF-4 is built up from monomeric entities in which bidentate thioguaninato ligands establish complementary hydrogen bonding interactions in non-coplanar directions leading to supramolecular layers that are further connected resulting in a porous structure with one-dimensional (1D) channels. The hydrogen bonding interactions among Watson鈥揅rick and sugar edges of monomeric entities in SMOF-5 give rise to a triply interpenetrated supramolecular framework. Octameric clusters in SMOF-7 are self-assembled by hydrogen bonding to yield a porous 3D network. SMOF-8 is built up from tetranuclear units that are linked via base pairing interactions involving Watson鈥揅rick faces to afford layers whose assembly generates a two-dimensional pore system. SMOF-9 is in between pure MOFs and SMOFs since it consists of 1D infinite coordination polymers held together by complementary hydrogen bonding interactions into a 3D supramolecular porous structure.}