Quadruply Bonded Dimolybdenum Atoms Surrounded by Dendrons:  Preparation, Characterization, and Electrochemistry

Liwporncharoenvong, Teerayuth; Luck, Rudy L.

doi:10.1021/ja0155130

Cited by 18 publications

(10 citation statements)

References 32 publications

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“…The signals from the aromatic protons are in the range of 6.24 to 6.50 ppm. The electronic spectrum shows a strong band in the UV region corresponding to a LMCT transition and a weak band at 439 nm that can be assigned to the δ ⇀ δ* transition. , The absorptions of the δ ⇀ δ* transitions for Mo 2 (O 2 CCH 3 ) 4 and Mo 2 (DAniF) occur at 434 and 430 nm, respectively. , Finally, the cyclovoltammogram shows a reversible wave corresponding to a one-electron process at 292 mV. This value is between 465 mV for Mo 2 (O 2 CCH 3 ) 4 and 244 mV for Mo 2 (DAniF) 4 34 measured under similar conditions.…”

Section: Resultsmentioning

confidence: 95%

Modifying Electronic Communication in Dimolybdenum Units by Linkage Isomers of Bridged Oxamidate Dianions

et al. 2003

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Reactions of Mo(2)(O(2)CCH(3))(DAniF)(3), DAniF = N,N'-di-p-anisylformamidinate, with oxamidate dianions [ArNC(O)C(O)NAr](2-), Ar = C(6)H(5) and p-anisyl, give pairs of isomeric compounds where the [Mo(2)] units are bridged by the oxamidate anions. For the alpha isomers, the C-C unit of the dianion is nearly perpendicular to the Mo-Mo bonds, and these are essentially perpendicular to each other. For the beta isomers, the corresponding C-C unit and the Mo-Mo bonds are essentially parallel to each other. Each type of isomer is stable in solution. The electronic communication as measured by the DeltaE(1/2) for the oxidation of each of the Mo(2) units is significantly better for the beta isomers. This is supported also by the appearance of what is conventionally called an intervalence charge-transfer band in the near infrared region upon oxidation of the beta isomers but not the alpha isomers. Molecular mechanics and DFT calculations help explain the relative conformations in the alpha isomers and the relative energy differences between the alpha and beta isomers.

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Section: Resultsmentioning

confidence: 95%

Modifying Electronic Communication in Dimolybdenum Units by Linkage Isomers of Bridged Oxamidate Dianions

et al. 2003

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“…architectures and materials of functional features. In particular, the targeted CCDC search indicates the existence of several very interesting complex molecular motifs exhibiting multiple resorcinol groups [86][87][88][89][90][91][92][93]; they may be definitely considered as potential platforms for multisite anions receptors exploiting the synthons described in this manuscript. Advanced research in this direction is underway in our group.…”

Section: Discussionmentioning

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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“…Similar progressive encapsulation effects have been observed in dendrimers containing polyaryl ether dendrons surrounding either a Co 2ϩ core, 261 or a quadruply bonded Mo 2 4ϩ unit. 262 As far as the photophysical properties are concerned, dendrimers containing lanthanide ions have been investigated. The polylysin dendrimer 85 contains 18 internal amide groups, which can coordinate lanthanide ions, and 24 peripheral dansyl units which feature strong absorption bands in the near UV region and an intense fluorescence band in the visible region (λ em = 514 nm, Φ = 0.28, τ = 15 ns).…”

Section: Other Metal Unitsmentioning

confidence: 99%

6 Recent developments in photo- and redox-active dendrimers

Juris

2003

Annu. Rep. Prog. Chem., Sect. C: Phys. Chem.

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Quadruply Bonded Dimolybdenum Atoms Surrounded by Dendrons: Preparation, Characterization, and Electrochemistry

Cited by 18 publications

References 32 publications

Modifying Electronic Communication in Dimolybdenum Units by Linkage Isomers of Bridged Oxamidate Dianions

Modifying Electronic Communication in Dimolybdenum Units by Linkage Isomers of Bridged Oxamidate Dianions

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

6 Recent developments in photo- and redox-active dendrimers

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