A multivariate library of zirconia metal-organic frameworks with dissolved p-nitroaniline dipoles and concentration-dependent optical and dielectric response

Kyle R. Langlois; Yangyang Wang; Fnu Joshua; Wesley J. Newsome; Lei Zhai; James K. Harper; Fernando J. Uribe-Romo

doi:10.1039/d5ce00299k

A multivariate library of zirconia metal-organic frameworks with dissolved p-nitroaniline dipoles and concentration-dependent optical and dielectric response

Kyle R. Langlois
, Yangyang Wang
, Fnu Joshua
, Wesley J. Newsome
, Lei Zhai
, James K. Harper
, Fernando J. Uribe-Romo

Macromolecular Nanomaterials

Research output: Contribution to journal › Article › peer-review

1 Scopus citations

Abstract

In this work, we show how the combination of soluble non-polar and polar links allows for the preparation of multivariate metal-organic frameworks (MTV MOFs) that exhibit dipolar solid-solution behavior. We prepared a library of PIZOF-2 MOFs with varied concentrations of p-nitroaniline (PNA)-containing moiety embedded within the MTV links. This library forms a partial solid solution up to 30 mol% with input/output composition ratio of 0.536 ± 0.018. MOFs with x > 5 mol% PNA show concentration-dependent hypsochromic dipole-dipole coupling (H-coupling) in the solid-state UV-visible spectra. The MTV library also exhibits a dielectric relaxation event in the broadband dielectric spectra with activation enthalpies and entropies that vary with temperature and PNA content and follow linear Meyer-Neldel compensation relations.

Original language	English
Pages (from-to)	4463-4469
Number of pages	7
Journal	CrystEngComm
Volume	27
Issue number	26
DOIs	https://doi.org/10.1039/d5ce00299k
State	Published - Jun 10 2025

Funding

This work was supported by the National Science Foundation Office of Advanced Cyberstructure (Award# 2118201). Dielectric spectroscopy measurements were performed at the Oak Ridge National Laboratory's Center for Nanophase Materials Sciences, which is a DOE Office of Science User Facility.

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10.1039/d5ce00299k

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title = "A multivariate library of zirconia metal-organic frameworks with dissolved p-nitroaniline dipoles and concentration-dependent optical and dielectric response",

abstract = "In this work, we show how the combination of soluble non-polar and polar links allows for the preparation of multivariate metal-organic frameworks (MTV MOFs) that exhibit dipolar solid-solution behavior. We prepared a library of PIZOF-2 MOFs with varied concentrations of p-nitroaniline (PNA)-containing moiety embedded within the MTV links. This library forms a partial solid solution up to 30 mol\% with input/output composition ratio of 0.536 ± 0.018. MOFs with x > 5 mol\% PNA show concentration-dependent hypsochromic dipole-dipole coupling (H-coupling) in the solid-state UV-visible spectra. The MTV library also exhibits a dielectric relaxation event in the broadband dielectric spectra with activation enthalpies and entropies that vary with temperature and PNA content and follow linear Meyer-Neldel compensation relations.",

author = "Langlois, \{Kyle R.\} and Yangyang Wang and Fnu Joshua and Newsome, \{Wesley J.\} and Lei Zhai and Harper, \{James K.\} and Uribe-Romo, \{Fernando J.\}",

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AU - Langlois, Kyle R.

AU - Wang, Yangyang

AU - Joshua, Fnu

AU - Newsome, Wesley J.

AU - Zhai, Lei

AU - Harper, James K.

AU - Uribe-Romo, Fernando J.

PY - 2025/6/10

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AB - In this work, we show how the combination of soluble non-polar and polar links allows for the preparation of multivariate metal-organic frameworks (MTV MOFs) that exhibit dipolar solid-solution behavior. We prepared a library of PIZOF-2 MOFs with varied concentrations of p-nitroaniline (PNA)-containing moiety embedded within the MTV links. This library forms a partial solid solution up to 30 mol% with input/output composition ratio of 0.536 ± 0.018. MOFs with x > 5 mol% PNA show concentration-dependent hypsochromic dipole-dipole coupling (H-coupling) in the solid-state UV-visible spectra. The MTV library also exhibits a dielectric relaxation event in the broadband dielectric spectra with activation enthalpies and entropies that vary with temperature and PNA content and follow linear Meyer-Neldel compensation relations.

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A multivariate library of zirconia metal-organic frameworks with dissolved p-nitroaniline dipoles and concentration-dependent optical and dielectric response

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