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Heterometallic multinuclear nodes directing MOF electronic behavior.

ABSTRACT: Metal node engineering in combination with modularity, topological diversity, and porosity of metal-organic frameworks (MOFs) could advance energy and optoelectronic sectors. In this study, we focus on MOFs with multinuclear heterometallic nodes for establishing metal-property trends, i.e., connecting atomic scale changes with macroscopic material properties by utilization of inductively coupled plasma mass spectrometry, conductivity measurements, X-ray photoelectron and diffuse reflectance spectroscopies, and density functional theory calculations. The results of Bader charge analysis and studies employing the Voronoi-Dirichlet partition of crystal structures are also presented. As an example of frameworks with different nodal arrangements, we have chosen MOFs with mononuclear, binuclear, and pentanuclear nodes, primarily consisting of first-row transition metals, that are incorporated in HHTP-, BTC-, and NIP-systems, respectively (HHTP^3- = triphenylene-2,3,6,7,10,11-hexaone; BTC^3- = 1,3,5-benzenetricarboxylate; and NIP^2- = 5-nitroisophthalate). Through probing framework electronic profiles, we demonstrate structure-property relationships, and also highlight the necessity for both comprehensive analysis of trends in metal properties, and novel avenues for preparation of heterometallic multinuclear isoreticular structures, which are critical components for on-demand tailoring of properties in heterometallic systems.

SUBMITTER: Ejegbavwo OA

PROVIDER: S-EPMC8159452 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Heterometallic multinuclear nodes directing MOF electronic behavior.

Ejegbavwo Otega A OA Berseneva Anna A AA Martin Corey R CR Leith Gabrielle A GA Pandey Shubham S Brandt Amy J AJ Park Kyoung Chul KC Mathur Abhijai A Farzandh Sharfa S Klepov Vladislav V VV Heiser Brittany J BJ Chandrashekhar Mvs M Karakalos Stavros G SG Smith Mark D MD Phillpot Simon R SR Garashchuk Sophya S Chen Donna A DA Shustova Natalia B NB

Chemical science 20200627 28

Metal node engineering in combination with modularity, topological diversity, and porosity of metal-organic frameworks (MOFs) could advance energy and optoelectronic sectors. In this study, we focus on MOFs with multinuclear heterometallic nodes for establishing metal-property trends, <i>i.e.</i>, connecting atomic scale changes with macroscopic material properties by utilization of inductively coupled plasma mass spectrometry, conductivity measurements, X-ray photoelectron and diffuse reflectan ...[more]

PMID: 34123019

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Project description:Metal organic frameworks (MOFs) are widely used in drug carrier research due to their tunability. The properties of MOFs can be adjusted through incorporation of mono-substituents to obtain pharmaceutical carriers with excellent properties. In this study, different functional groups of -NH2, -CH3, -Br, -OH and -CH2[double bond, length as m-dash]CH are connected to MOF-5 to analyse the effect of mono-substituent incorporation on drug delivery properties. The resulting MOFs have similar structures, except for Br-MOF. The pore size of this series of MOFs ranges from 1.04 nm to 1.10 nm. Using oridonin (ORI) as a model drug, introduction of the functional groups appears to have a significant effect on the drug delivery performance of the MOFs. The IRMOFs can be ranked according to drug-loading capacity: MOF-5 > HO-MOF-5 > H3C-MOF-5 = Br-MOF-5 > H2N-MOF-5 > CH2[double bond, length as m-dash]CH-MOF-5. The ORI release from ORI @IRMOFs is explored at two different pH values: 7.4 and 5.5, and the ORI@IRMOFs are ranked according to the cumulative release percentage of ORI: ORI@MOF-5 > ORI@Br-MOF-5 > ORI@H3C-MOF-5 > ORI@H2N-MOF-5 > CH2[double bond, length as m-dash]CH-MOF-5 > ORI@ HO-MOF-5. In particular, the release behaviour of ORI@MOFs is described through a new model. The different drug delivery performance of MOFs may be due to the complex interactions between MOFs and ORI. In addition, the introduction of single substituents does not change the biocompatibility of MOFs. MTT in vitro experiments prove that this series of MOFs has low cytotoxicity. This study shows that the incorporation of single substituents can effectively adjust the drug delivery behaviour of MOFs, which is conducive to realization of personalized drug delivery modes. The introduction of active groups can also facilitate post-synthesis modification to achieve coupling of targeting groups. MOFs incorporated with single substituents perform favorably in terms of use as biomedical drug delivery alternative carriers in effective drug payload and flexible drug release.

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Heterometallic multinuclear nodes directing MOF electronic behavior.

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Heterometallic multinuclear nodes directing MOF electronic behavior.

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