Beyond π-π Stacking: Understanding Inversion Symmetry Breaking in Crystalline Racemates

Yiran Wang; Matthew L. Nisbet; Kendall R. Kamp; Emily Hiralal; Romain Gautier; P. Shiv Halasyamani; Kenneth R. Poeppelmeier

doi:10.1021/jacs.3c05380

Beyond π-π Stacking: Understanding Inversion Symmetry Breaking in Crystalline Racemates

Yiran Wang, Matthew L. Nisbet, Kendall R. Kamp, Emily Hiralal, Romain Gautier, P. Shiv Halasyamani, Kenneth R. Poeppelmeier^*

^*Corresponding author for this work

Chemistry

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

8 Scopus citations

Abstract

The design of noncentrosymmetric (NCS) solid state materials, specifically how to break inversion symmetry between enantiomers, has intrigued chemists, physicists, and materials scientists for many years. Because the chemical complexity of molecular racemic building units is so varied, targeting these materials is poorly understood. Previously, three isostructural racemic compounds with a formula of [Cu(H₂O)(bpy)₂]₂[MF₆]₂·2H₂O (bpy = 2,2’=bipyridine; M = Ti, Zr, Hf) were shown to crystallize in the NCS space group Pna2₁, of polar, achiral crystal class mm2. In this work, we synthesized five new racemic compounds with the formula [Cu(H₂O)(dmbpy)₂]₂[MF₆]₂·xH₂O (dmbpy = 4,4′/5,5′-dimethyl-2,2′-bipyridine; M = Ti, Zr, Hf). Single crystal X-ray diffraction reveals that the five newly synthesized compounds feature equimolar combinations of Δ- and Λ-Cu(dmbpy)₂(H₂O)²⁺ complexes that are assembled into packing motifs similar to those found in the reported NCS structure but all crystallize in centrosymmetric (CS) space groups. Seven structural descriptors were created to analyze the intermolecular interactions on the assembly of Cu racemates in the CS and NCS structures. The structural analysis reveals that in the CS structures, the inversion center results from parallel heterochiral π-π stacking interactions between adjacent Cu racemates regardless of cation geometries, hydrogen bonding networks, or interlayer architectures, whereas in the NCS structure, nonparallel heterochiral π-π interactions between the adjacent Cu racemates preclude an inversion center. The parallel heterochiral π-π interactions in the CS structures can be rationalized by the restrained geometries of the methyl-substituted ligands. This work demonstrates that the introduction of nonparallel stacking can suppress the formation of an inversion center for an NCS racemate. A conceptual framework and practical approach linking the absence of inversion symmetry in racemates is presented for all NCS crystal classes.

Original language	English (US)
Pages (from-to)	16879-16888
Number of pages	10
Journal	Journal of the American Chemical Society
Volume	145
Issue number	30
DOIs	https://doi.org/10.1021/jacs.3c05380
State	Published - Aug 2 2023

Funding

This work was supported by fundings from the National Science Foundation (DMR-1904701). PSH thanks the Welch Foundation (Grant E-1457) and the National Science Foundation (DMR-2002319) for support. Single-crystal X-ray diffraction data were acquired at IMSERC at Northwestern University, which has received support from the Soft and Hybrid Nanotechnology Experimental (SHyNE) Resource (NSF ECCS-1542205), the State of Illinois, the International Institute for Nanotechnology (IIN), and the National Science Foundation (DMR-0521267). The authors thank Dr. C. D. Malliakas and Ms. C. Stern for experimental assistance.

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/jacs.3c05380

Cite this

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title = "Beyond π-π Stacking: Understanding Inversion Symmetry Breaking in Crystalline Racemates",

abstract = "The design of noncentrosymmetric (NCS) solid state materials, specifically how to break inversion symmetry between enantiomers, has intrigued chemists, physicists, and materials scientists for many years. Because the chemical complexity of molecular racemic building units is so varied, targeting these materials is poorly understood. Previously, three isostructural racemic compounds with a formula of [Cu(H2O)(bpy)2]2[MF6]2·2H2O (bpy = 2,2{\textquoteright}=bipyridine; M = Ti, Zr, Hf) were shown to crystallize in the NCS space group Pna21, of polar, achiral crystal class mm2. In this work, we synthesized five new racemic compounds with the formula [Cu(H2O)(dmbpy)2]2[MF6]2·xH2O (dmbpy = 4,4′/5,5′-dimethyl-2,2′-bipyridine; M = Ti, Zr, Hf). Single crystal X-ray diffraction reveals that the five newly synthesized compounds feature equimolar combinations of Δ- and Λ-Cu(dmbpy)2(H2O)2+ complexes that are assembled into packing motifs similar to those found in the reported NCS structure but all crystallize in centrosymmetric (CS) space groups. Seven structural descriptors were created to analyze the intermolecular interactions on the assembly of Cu racemates in the CS and NCS structures. The structural analysis reveals that in the CS structures, the inversion center results from parallel heterochiral π-π stacking interactions between adjacent Cu racemates regardless of cation geometries, hydrogen bonding networks, or interlayer architectures, whereas in the NCS structure, nonparallel heterochiral π-π interactions between the adjacent Cu racemates preclude an inversion center. The parallel heterochiral π-π interactions in the CS structures can be rationalized by the restrained geometries of the methyl-substituted ligands. This work demonstrates that the introduction of nonparallel stacking can suppress the formation of an inversion center for an NCS racemate. A conceptual framework and practical approach linking the absence of inversion symmetry in racemates is presented for all NCS crystal classes.",

author = "Yiran Wang and Nisbet, {Matthew L.} and Kamp, {Kendall R.} and Emily Hiralal and Romain Gautier and Halasyamani, {P. Shiv} and Poeppelmeier, {Kenneth R.}",

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AU - Nisbet, Matthew L.

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AU - Hiralal, Emily

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AU - Halasyamani, P. Shiv

AU - Poeppelmeier, Kenneth R.

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N2 - The design of noncentrosymmetric (NCS) solid state materials, specifically how to break inversion symmetry between enantiomers, has intrigued chemists, physicists, and materials scientists for many years. Because the chemical complexity of molecular racemic building units is so varied, targeting these materials is poorly understood. Previously, three isostructural racemic compounds with a formula of [Cu(H2O)(bpy)2]2[MF6]2·2H2O (bpy = 2,2’=bipyridine; M = Ti, Zr, Hf) were shown to crystallize in the NCS space group Pna21, of polar, achiral crystal class mm2. In this work, we synthesized five new racemic compounds with the formula [Cu(H2O)(dmbpy)2]2[MF6]2·xH2O (dmbpy = 4,4′/5,5′-dimethyl-2,2′-bipyridine; M = Ti, Zr, Hf). Single crystal X-ray diffraction reveals that the five newly synthesized compounds feature equimolar combinations of Δ- and Λ-Cu(dmbpy)2(H2O)2+ complexes that are assembled into packing motifs similar to those found in the reported NCS structure but all crystallize in centrosymmetric (CS) space groups. Seven structural descriptors were created to analyze the intermolecular interactions on the assembly of Cu racemates in the CS and NCS structures. The structural analysis reveals that in the CS structures, the inversion center results from parallel heterochiral π-π stacking interactions between adjacent Cu racemates regardless of cation geometries, hydrogen bonding networks, or interlayer architectures, whereas in the NCS structure, nonparallel heterochiral π-π interactions between the adjacent Cu racemates preclude an inversion center. The parallel heterochiral π-π interactions in the CS structures can be rationalized by the restrained geometries of the methyl-substituted ligands. This work demonstrates that the introduction of nonparallel stacking can suppress the formation of an inversion center for an NCS racemate. A conceptual framework and practical approach linking the absence of inversion symmetry in racemates is presented for all NCS crystal classes.

AB - The design of noncentrosymmetric (NCS) solid state materials, specifically how to break inversion symmetry between enantiomers, has intrigued chemists, physicists, and materials scientists for many years. Because the chemical complexity of molecular racemic building units is so varied, targeting these materials is poorly understood. Previously, three isostructural racemic compounds with a formula of [Cu(H2O)(bpy)2]2[MF6]2·2H2O (bpy = 2,2’=bipyridine; M = Ti, Zr, Hf) were shown to crystallize in the NCS space group Pna21, of polar, achiral crystal class mm2. In this work, we synthesized five new racemic compounds with the formula [Cu(H2O)(dmbpy)2]2[MF6]2·xH2O (dmbpy = 4,4′/5,5′-dimethyl-2,2′-bipyridine; M = Ti, Zr, Hf). Single crystal X-ray diffraction reveals that the five newly synthesized compounds feature equimolar combinations of Δ- and Λ-Cu(dmbpy)2(H2O)2+ complexes that are assembled into packing motifs similar to those found in the reported NCS structure but all crystallize in centrosymmetric (CS) space groups. Seven structural descriptors were created to analyze the intermolecular interactions on the assembly of Cu racemates in the CS and NCS structures. The structural analysis reveals that in the CS structures, the inversion center results from parallel heterochiral π-π stacking interactions between adjacent Cu racemates regardless of cation geometries, hydrogen bonding networks, or interlayer architectures, whereas in the NCS structure, nonparallel heterochiral π-π interactions between the adjacent Cu racemates preclude an inversion center. The parallel heterochiral π-π interactions in the CS structures can be rationalized by the restrained geometries of the methyl-substituted ligands. This work demonstrates that the introduction of nonparallel stacking can suppress the formation of an inversion center for an NCS racemate. A conceptual framework and practical approach linking the absence of inversion symmetry in racemates is presented for all NCS crystal classes.

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Beyond π-π Stacking: Understanding Inversion Symmetry Breaking in Crystalline Racemates

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CCDC 2264648: Experimental Crystal Structure Determination

CCDC 2264645: Experimental Crystal Structure Determination

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Beyond π-π Stacking: Understanding Inversion Symmetry Breaking in Crystalline Racemates

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ASJC Scopus subject areas

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CCDC 2264648: Experimental Crystal Structure Determination

CCDC 2264645: Experimental Crystal Structure Determination

CCDC 2264646: Experimental Crystal Structure Determination

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