Tetrazine Chromophore-Based Metal-Organic Frameworks with Unusual Configurations: Synthetic, Structural, Theoretical, Fluorescent, and Nonlinear Optical Studies

Jianghua Li; Ding Jia; Suci Meng; Jinfang Zhang; Marie Cifuentes; Mark Humphrey; Chi Zhang

doi:10.1002/chem.201404803

Tetrazine Chromophore-Based Metal-Organic Frameworks with Unusual Configurations: Synthetic, Structural, Theoretical, Fluorescent, and Nonlinear Optical Studies

Jianghua Li, Ding Jia, Suci Meng, Jinfang Zhang, Marie Cifuentes, Mark Humphrey, Chi Zhang

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

Abstract

Three unusual three-dimensional (3D) tetrazine chromophore-based metal-organic frameworks (MOFs) {(Et<inf>4</inf>N)[WS<inf>4</inf>Cu<inf>3</inf>(CN)<inf>2</inf>(4,4-pytz)<inf>0.5</inf>]}<inf>n</inf> (1), {[MoS<inf>4</inf>Cu<inf>4</inf>(CN)<inf>2</inf>(4,4-pytz)<inf>2</inf>]{dot operator}CH<inf>2</inf>Cl<inf>2</inf>}<inf>n</inf> (2), and {[WS<inf>4</inf>Cu<inf>3</inf>(4,4-pytz)<inf>3</inf>]{dot operator}[N(CN)<inf>2</inf>]}<inf>n</inf> (3; 4,4-pytz=3,6-bis(4-pyridyl)tetrazine) have been synthesized and characterized by using FTIR and UV/Vis spectroscopy, elemental analysis, powder X-ray diffraction, gel permeation chromatography, steady-state fluorescence, and thermogravimetric analysis; their identities were confirmed by single-crystal X-ray diffraction studies. MOF 1 possesses the first five-connected M/S/Cu (M=Mo, W) framework with an unusual 3D (44{dot operator}66) topology constructed from T-shaped [WS<inf>4</inf>Cu<inf>3</inf>]+ clusters as nodes and single CN-/4,4-pytz bridges as linkers. MOF 2 features a novel 3D MOF structure with (420{dot operator}68) topology, in which the bridging 4,4-pytz ligands exhibit unique distorted arch structures. MOF 3 displays the first 3D MOF structure based on flywheel-shaped [WS<inf>4</inf>Cu<inf>3</inf>]+ clusters with a non-interpenetrating honeycomb-like framework and a heavily distorted "ACS" topology. Steady-state fluorescence studies of 1-3 reveal significant fluorescence emissions. The nonlinear optical (NLO) properties of 1-3 were investigated by using a Z-scan technique with 5ns pulses at Î»=532nm. The Z-scan experimental results show that the Ï€-delocalizable tetrazine-based 4,4-pytz ligands contribute to the strong third-order NLO properties exhibited by 1-3. Time-dependent density functional theory studies afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials.

Original language	English
Pages (from-to)	7914-7926
Journal	Chemistry, A European Journal
Volume	21
Issue number	21
DOIs	https://doi.org/10.1002/chem.201404803
Publication status	Published - 2015

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@article{f6c79d5cee364303abe19fc332b496df,

title = "Tetrazine Chromophore-Based Metal-Organic Frameworks with Unusual Configurations: Synthetic, Structural, Theoretical, Fluorescent, and Nonlinear Optical Studies",

abstract = "Three unusual three-dimensional (3D) tetrazine chromophore-based metal-organic frameworks (MOFs) {(Et4N)[WS4Cu3(CN)2(4,4-pytz)0.5]}n (1), {[MoS4Cu4(CN)2(4,4-pytz)2]{dot operator}CH2Cl2}n (2), and {[WS4Cu3(4,4-pytz)3]{dot operator}[N(CN)2]}n (3; 4,4-pytz=3,6-bis(4-pyridyl)tetrazine) have been synthesized and characterized by using FTIR and UV/Vis spectroscopy, elemental analysis, powder X-ray diffraction, gel permeation chromatography, steady-state fluorescence, and thermogravimetric analysis; their identities were confirmed by single-crystal X-ray diffraction studies. MOF 1 possesses the first five-connected M/S/Cu (M=Mo, W) framework with an unusual 3D (44{dot operator}66) topology constructed from T-shaped [WS4Cu3]+ clusters as nodes and single CN-/4,4-pytz bridges as linkers. MOF 2 features a novel 3D MOF structure with (420{dot operator}68) topology, in which the bridging 4,4-pytz ligands exhibit unique distorted arch structures. MOF 3 displays the first 3D MOF structure based on flywheel-shaped [WS4Cu3]+ clusters with a non-interpenetrating honeycomb-like framework and a heavily distorted {"}ACS{"} topology. Steady-state fluorescence studies of 1-3 reveal significant fluorescence emissions. The nonlinear optical (NLO) properties of 1-3 were investigated by using a Z-scan technique with 5ns pulses at {\^I}»=532nm. The Z-scan experimental results show that the {\"I}€-delocalizable tetrazine-based 4,4-pytz ligands contribute to the strong third-order NLO properties exhibited by 1-3. Time-dependent density functional theory studies afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials.",

author = "Jianghua Li and Ding Jia and Suci Meng and Jinfang Zhang and Marie Cifuentes and Mark Humphrey and Chi Zhang",

year = "2015",

doi = "10.1002/chem.201404803",

language = "English",

volume = "21",

pages = "7914--7926",

journal = "Chemistry, A European Journal",

publisher = "Wiley-VCH Verlag GmbH",

number = "21",

}

TY - JOUR

T1 - Tetrazine Chromophore-Based Metal-Organic Frameworks with Unusual Configurations: Synthetic, Structural, Theoretical, Fluorescent, and Nonlinear Optical Studies

AU - Li, Jianghua

AU - Jia, Ding

AU - Meng, Suci

AU - Zhang, Jinfang

AU - Cifuentes, Marie

AU - Humphrey, Mark

AU - Zhang, Chi

PY - 2015

Y1 - 2015

N2 - Three unusual three-dimensional (3D) tetrazine chromophore-based metal-organic frameworks (MOFs) {(Et4N)[WS4Cu3(CN)2(4,4-pytz)0.5]}n (1), {[MoS4Cu4(CN)2(4,4-pytz)2]{dot operator}CH2Cl2}n (2), and {[WS4Cu3(4,4-pytz)3]{dot operator}[N(CN)2]}n (3; 4,4-pytz=3,6-bis(4-pyridyl)tetrazine) have been synthesized and characterized by using FTIR and UV/Vis spectroscopy, elemental analysis, powder X-ray diffraction, gel permeation chromatography, steady-state fluorescence, and thermogravimetric analysis; their identities were confirmed by single-crystal X-ray diffraction studies. MOF 1 possesses the first five-connected M/S/Cu (M=Mo, W) framework with an unusual 3D (44{dot operator}66) topology constructed from T-shaped [WS4Cu3]+ clusters as nodes and single CN-/4,4-pytz bridges as linkers. MOF 2 features a novel 3D MOF structure with (420{dot operator}68) topology, in which the bridging 4,4-pytz ligands exhibit unique distorted arch structures. MOF 3 displays the first 3D MOF structure based on flywheel-shaped [WS4Cu3]+ clusters with a non-interpenetrating honeycomb-like framework and a heavily distorted "ACS" topology. Steady-state fluorescence studies of 1-3 reveal significant fluorescence emissions. The nonlinear optical (NLO) properties of 1-3 were investigated by using a Z-scan technique with 5ns pulses at Î»=532nm. The Z-scan experimental results show that the Ï€-delocalizable tetrazine-based 4,4-pytz ligands contribute to the strong third-order NLO properties exhibited by 1-3. Time-dependent density functional theory studies afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials.

AB - Three unusual three-dimensional (3D) tetrazine chromophore-based metal-organic frameworks (MOFs) {(Et4N)[WS4Cu3(CN)2(4,4-pytz)0.5]}n (1), {[MoS4Cu4(CN)2(4,4-pytz)2]{dot operator}CH2Cl2}n (2), and {[WS4Cu3(4,4-pytz)3]{dot operator}[N(CN)2]}n (3; 4,4-pytz=3,6-bis(4-pyridyl)tetrazine) have been synthesized and characterized by using FTIR and UV/Vis spectroscopy, elemental analysis, powder X-ray diffraction, gel permeation chromatography, steady-state fluorescence, and thermogravimetric analysis; their identities were confirmed by single-crystal X-ray diffraction studies. MOF 1 possesses the first five-connected M/S/Cu (M=Mo, W) framework with an unusual 3D (44{dot operator}66) topology constructed from T-shaped [WS4Cu3]+ clusters as nodes and single CN-/4,4-pytz bridges as linkers. MOF 2 features a novel 3D MOF structure with (420{dot operator}68) topology, in which the bridging 4,4-pytz ligands exhibit unique distorted arch structures. MOF 3 displays the first 3D MOF structure based on flywheel-shaped [WS4Cu3]+ clusters with a non-interpenetrating honeycomb-like framework and a heavily distorted "ACS" topology. Steady-state fluorescence studies of 1-3 reveal significant fluorescence emissions. The nonlinear optical (NLO) properties of 1-3 were investigated by using a Z-scan technique with 5ns pulses at Î»=532nm. The Z-scan experimental results show that the Ï€-delocalizable tetrazine-based 4,4-pytz ligands contribute to the strong third-order NLO properties exhibited by 1-3. Time-dependent density functional theory studies afforded insight into the electronic transitions and spectral characterization of these functionalized NLO molecular materials.

U2 - 10.1002/chem.201404803

DO - 10.1002/chem.201404803

M3 - Article

VL - 21

SP - 7914

EP - 7926

JO - Chemistry, A European Journal

JF - Chemistry, A European Journal

IS - 21

ER -

Tetrazine Chromophore-Based Metal-Organic Frameworks with Unusual Configurations: Synthetic, Structural, Theoretical, Fluorescent, and Nonlinear Optical Studies

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