A concerted evolution of supramolecular interactions in a {cation; metal complex; π-acid; solvent} anion-π system

Kuzniak-Glanowska, Emilia; Hooper, James; Srebro‐Hooper, Monika; Kobylarczyk, Jedrzej; Dziurka, Magdalena; Musielak, Bogdan; Pinkowicz, Dawid; Raya, Jésus; Ferlay, Sylvie; Podgajny, Robert

doi:10.1039/d0qi00101e

Cited by 9 publications

(9 citation statements)

References 63 publications

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“…The molecular environment of the tectons engaged in the hydrogen-bond networks is completed by the oligomeric arrays of PPh 4 + cations accompanied by some MeCN molecules; these components form multiple weak C-H•••A interactions (A = O atoms and ring system of H 3 PG, N atoms of [M(CN) 6 ] 3− ) in the regions not involved in the typical hydrogen bonds (Figure S3). The {PPh 4 + } ∞ 3D subnetwork itself provides substantial structural stabilization through so-called multiple phenyl embrace (MPE) motifs, here realized mainly by the sextuple phenyl embrace (SPE) or offset sextuple phenyl embrace (OSPE) and other hybrid patterns, with the shortest P•••P distances of 6.2, 6.6, and 7.3 Å in all structures [51,52] (Figure S4).…”

Section: Structural Studiesmentioning

confidence: 99%

Supramolecular cis-“Bis(Chelation)” of [M(CN)6]3− (M = CrIII, FeIII, CoIII) by Phloroglucinol (H3PG)

et al. 2022

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Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure–properties–application schemes. Co-crystal salts involving anionic d-metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh4)3[M(CN)6](H3PG)2·2MeCN (M = Cr, 1; Fe, 2; Co 3; H3PG = phloroglucinol, 1,3,5-trihydroxobenzene). In this study, 1–3 were characterized experimentally using SC XRD, Hirshfeld analysis, ESI-MS spectrometry, vibrational IR and Raman, 57Fe Mössbauer, electronic absorption UV-Vis-NIR, and photoluminescence spectroscopies, and theoretically with density functional theory calculations. The two-dimensional square grid-like hydrogen-bond {[M(CN)6]3–;(H3PG)2}¥ network features original {[M(CN)6]3–;(H3PG)4} supramolecular cis-bis(chelate) motifs involving: (i) two double cyclic hydrogen bond synthons M(-CN×××HO-)2Ar, {[M(CN)6]3–;H2PGH}, between cis-oriented cyanido ligands of [M(CN)6]3– and resorcinol-like face of H3PG, and (ii) two single hydrogen bonds M-CN×××HO-Ar, {[M(CN)6]3–;HPGH2}, involving the remaining two cyanide ligands. The occurrence of the above tectonic motif is discussed with regard to the relevant data existing in the CCDC database, including the multisite H-bond binding of [M(CN)6]3– by organic species, mononuclear coordination complexes, and polynuclear complexes. The physicochemical and computational characterization discloses notable spectral modifications under the regime of an extended hydrogen bond network.

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Section: Structural Studiesmentioning

confidence: 99%

Supramolecular cis-“Bis(Chelation)” of [M(CN)6]3− (M = CrIII, FeIII, CoIII) by Phloroglucinol (H3PG)

et al. 2022

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“…The above observations are also in line with results presented in previous studies where structural analyses and detailed computational analyses of simple anion-π systems revealed that parallel anion orientations are preferred due to overlapping orbitals and their contribution to overall stabilization. 20,21,[70][71][72] Nevertheless, atypical angle distributions are observed in region A for such ions as citric acid, where no orientation is privileged, and the carboxylic group of heme strongly prefers edgewise geometry.…”

Section: Anion-ring Pair In Sequence -Secondary Structure Correlationsmentioning

confidence: 99%

“…Thus, canonical anion-π synthons reveal their significance in performance of advanced small-molecule catalytic systems dedicated to specific organic reactions, [1][2][3] photophysical systems based on charge or electron transfer properties, [4][5][6][7][8][9] anion recognition, binding, and sensing, [10][11][12][13] anion transport, [14][15][16][17] or anion directed self-assembly of polynuclear coordination complexes. 18 Further on, the new generation supramolecular and coordination anion-π architectures hosting mononuclear 8,[19][20][21] and polynuclear d-metalate complexes 9,22,23 were recently reported in the context of anion binding, 19,20 molecular crystalline composites, 21 charge transfer and photophysical properties, 8,9,[20][21][22] or magnetic properties. 23 In parallel, edgewise cooperative synthons that exploit multiple side ringC-Hanion contacts at the ring edge are well known to stabilise numerous molecular architectures.…”

Section: Introductionmentioning

confidence: 99%

Mining anion–aromatic interactions in the Protein Data Bank

et al. 2022

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“…The molecules in Chart are strong electron acceptors with reduction potentials of −0.20, 0.02, and 0.56 V vs SCE for TCP, FA, and DDQ, respectively. , The literature data indicated the propensity of these neutral π-acceptors to binding (pseudo)-halides, metal halides, and other anions. ,,,, In particular, the study of complexes of TCP with halide (Cl – , Br – , and I – ) anions provided evidence of anion−π bonding in solution and the solid state . The Mulliken dependence of the energy of the absorption bands, which was observed for the complexes of TCP and p -benzoquinones with (pseudo-)halides suggested the charge transfer nature of such associations. , In the systems in which the strongest π-acceptors (e.g., DDQ) were combined with the I – or Br – anions (which are rather strong electron donors), the formation of the charge-transfer complexes was followed by electron transfer …”

Section: Introductionmentioning

confidence: 98%

“…20,32 The literature data indicated the propensity of these neutral π-acceptors to binding (pseudo)-halides, metal halides, and other anions. 18,20,21,33,34 In particular, the study of complexes of TCP with halide (Cl − , Br − , and I − ) anions provided evidence of anion−π bonding in solution and the solid state. 18 The Mulliken dependence of the energy of the absorption bands, which was observed for the complexes of TCP and pbenzoquinones with (pseudo-)halides suggested the charge transfer nature of such associations.…”

Section: Introductionmentioning

confidence: 99%

Exploring the Nature of Anion−π Interactions: Complexes of π-Acceptors with Fluoro- or Oxoanions Compared to the Associations with Halides

Odubo,

Zeller,

Rosokha

2023

J. Phys. Chem. A

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The variations in the nature and properties of the anion−π complexes with different types of anions are identified via experimental (UV–vis and X-ray crystallographic) measurements and computational analysis of the associations of tetracyanopyrazine, tetrafluoro-, or dichlorodicyano-p-benzoquinone. Co-crystals of these π-acceptors with the salts of fluoro- and oxoanions (PF6 –, BF4 –, CF3SO3 –, or ClO4 –) comprised anion−π bonded alternating chains or 1:2 complexes showing interatomic contacts of up to 15% shorter than the van der Waals separations. DFT computations confirmed that binding energies between the neutral π-acceptors and polyatomic noncoordinating oxo- and fluoroanions are comparable to those in the previously reported anion−π complexes with more nucleophilic halides. Yet, while the latter show distinct charge-transfer bands in the UV–vis range, the absorption spectra of the solutions containing oxo- and fluoroanions and the π-acceptors were close to those of the individual reactants. The natural bond orbital (NBO) analysis revealed a very small charge transfer of Δq = 0.01–0.02 e in the complexes with oxo- or fluoroanions as compared to the Δq = 0.05–0.22 e found for analogous complexes with halides. These distinctions were related to the smaller frontier orbital energy gap and better overlap in the complexes with halides (since the highest occupied orbitals of these monoatomic anions are closer in energy to the lowest unoccupied orbitals of the π-acceptors) as compared to that in the multicenter-bonded associations with polyatomic oxo- and fluoroanions. In accordance with these data, the energy decomposition analysis showed that while the complexes of neutral π-acceptors with the fluoro- and oxoanions are formed predominantly via electrostatic interaction, the associations with halides comprised significant orbital (charge-transfer) interactions and they explain their spectral and structural features.

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A concerted evolution of supramolecular interactions in a {cation; metal complex; π-acid; solvent} anion-π system

Abstract: Comprehensive studies on a concerted evolution of supramolecular interactions with multicomponent synthon reproduction provide a new tool to describe the trapping of flat [M(L)4]2− complexes within π-acidic cavities.

Cited by 9 publications

References 63 publications

Supramolecular cis-“Bis(Chelation)” of [M(CN)6]3− (M = CrIII, FeIII, CoIII) by Phloroglucinol (H3PG)

Supramolecular cis-“Bis(Chelation)” of [M(CN)6]3− (M = CrIII, FeIII, CoIII) by Phloroglucinol (H3PG)

Mining anion–aromatic interactions in the Protein Data Bank

Exploring the Nature of Anion−π Interactions: Complexes of π-Acceptors with Fluoro- or Oxoanions Compared to the Associations with Halides

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