Toward a dodecanuclear molecular Re(<scp>i</scp>) box: structural and spectroscopic properties

Tzeng, Biing‐Chiau; Hsiao, Y.Y.; Lee, Gene‐Hsiang; Wang, Haiying; Leong, Chanel F.; D’Alessandro, Deanna M.; Zuo, Jing‐Lin

doi:10.1039/c9dt01115c

Cited by 3 publications

(7 citation statements)

References 33 publications

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“…It is noted that the low-energy emissions at ca . 561 and 534 nm for complexes 1 and 2 , respectively, are suggestive of a metal-to-ligand charge-transfer (MLCT) transition in origin, where similar assignments have been made in our previous dipyridyl, tripyridyl, and tetrapyridyl systems …”

Section: Resultssupporting

confidence: 82%

“…In complex 1 , two [(Re(CO) 3 ) 3 (C 3 N 3 S 3 )] moieties form a supramolecular trigonal-prismatic structure through three bifurcated hydrogen bonds between their carboxylic acid moieties Py-4-COOH (i.e., O···O 2.585 (18)–2.711 (16) Å), and the simplified supramolecular trigonal prism is shown in Figure c, where each hydrogen-bonded dimer contains an intramolecular Re(I)···Re(I) av separation of 6.04 Å as well as a dihedral angle of 4.14° between the two Re(I) triangles. The dihedral angle of 4.14° is comparable to the values of 0.57–3.33° found in [(Re(CO) 3 ) 6 ( L ) 3 (C 3 N 3 S 3 ) 2 ], indicative of almost a parallel trigonal prism. Moreover, the length of the trigonal prism within a hydrogen-bonded dimer is calculated to be ca .…”

Section: Resultssupporting

confidence: 75%

“…Unlike complex 1 , two [(Re(CO) 3 ) 3 (C 3 N 3 S 3 )] moieties form a supramolecular trigonal-antiprismatic structure through three bifurcated hydrogen bonds between their carboxylic acid moieties, Pybz-4-COOH (i.e., O···O 2.577(4)-2.700 (4) Å) for complex 2 . Each hydrogen-bonded dimer contains an intramolecular Re(I)···Re(I) av separation of 6.04 Å and a dihedral angle of 4.28° between the two Re(I) triangles, which are similar to those of complex 1 and our reported cages, indicative of almost a parallel trigonal-antiprism structure as well. In addition, the length of the trigonal antiprism within a hydrogen-bonded dimer is calculated to be ca .…”

Section: Resultssupporting

confidence: 73%

“…A series of molecular boxes were previously constructed based on a versatile building block of [(Re(CO) 4 ) 3 (C 3 N 3 S 3 )] with various linear dipyridyl (pyrazine (pz), 4,4′-bipyridine (bpy), 1,2-di(4-pyridyl)ethylene (dpe), bis(4-pyridyl)acetylene (bpa), and 1,4-bis(pyridyl-4-ylethynyl)benzene (bpb)) and tripyridyl (1,3,5-tris(4-pyridylethynyl)benzene (tpb)) ligands by our group . Interestingly, various trigonal-prismatic structures of [(Re(CO) 3 ) 6 ( L ) 3 (C 3 N 3 S 3 ) 2 ] ( L = pz, bpy, bpe, bpa, and bpb)can be systematically tuned and synthesized, and moreover, a rare nonanuclear box of [(Re(CO) 3 ) 9 (tpb) 3 (C 3 N 3 S 3 ) 3 ] involving the tripyridyl ligand (tpb) can be also isolated as a remarkable trianglular-star structure .…”

Section: Introductionmentioning

confidence: 99%

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Toward Heteronuclear Molecular Re(I)-Cu(II) Boxes: Structural, Luminescent, and Magnetic Properties

et al. 2021

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The bifunctional ligands of isonicotinic acid (Py-4-COOH) and 4-pyrid-4-ylbenzoic acid (Pybz-4-COOH) instead of polypyridines were therefore reacted with (Re(CO) 4 ) 3 (C 3 N 3 S 3 ) (C 3 N 3 S 3 = cyanurate trianion), resulting in the formation of two trinuclear [(Re(CO) 3 ) 3 (C 3 N 3 S 3 )(Py-4-COOH) 3 ] (1) and [(Re-(CO) 3 ) 3 (C 3 N 3 S 3 )(Pybz-4-COOH) 3 ] (2), respectively. In the meantime, both complexes 1 and 2 are connected by three bifurcated hydrogen bonds between their carboxylic acid moieties Py-4-COOH and Pybz-4-COOH to form the supramolecular trigonal-prismatic and -antiprismatic structures, respectively. It is noted that complex 1 can further react with copper(II) nitrate upon deprotonation to give nonanuclear [(Re(CO) 3 ) 3 (C 3 N 3 S 3 )(Py-4-COO) 3 ] 2 Cu 3 (H 2 O) 9 (3), where two trinuclear [(Re(CO) 3 ) 3 (C 3 N 3 S 3 )(Py-4-COO) 3 ] moieties are connected by three penta-coordinate copper(II) ions, each coordinating to two carboxylates and three water molecules, to form the trigonal-prismatic structure. Surprisingly, addition of pyrazine (pz) in the synthetic process of complex 3 resulted in serendipitous isolation of a rare example of octadecanuclear {[(Re(CO) 3 ) 3 (C 3 N 3 S 3 )(Py-4-COO) 3 ] 2 Cu 3 (H 2 O) 6 (pz) 2 } 2 (4), which can be regarded as a dimer of complex 3, connected by two bridging pz ligands. Interestingly, both complexes 3 and 4 are heteronuclear molecular Re(I)-Cu(II) boxes, constructed by a complex-as-a-ligand strategy. Furthermore, complexes 1 and 2 can exhibit respective low-energy luminescence at ca. 561 and 534 nm at room temperature upon photoexcitation, and complex 3 is found to display antiferromagnetic coupling of −127.68 and −134.70 cm −1 , possibly due to multiple hydrogen bonds inducing significant Cu(II)•••Cu(II) coupling.

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Section: Resultssupporting

confidence: 82%

Section: Resultssupporting

confidence: 75%

Section: Resultssupporting

confidence: 73%

Section: Introductionmentioning

confidence: 99%

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Toward Heteronuclear Molecular Re(I)-Cu(II) Boxes: Structural, Luminescent, and Magnetic Properties

et al. 2021

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“…Recently, 1p was employed for the synthesis of a dodecanuclear molecular rhenium box that displays luminescence in the solid state. 25 Compound 1p can also be used to construct redox-active MOFs 26 and is expected to find additional applications in coordination chemistry as a neutral ligand complementary to tetraanionic TTFTB.…”

Section: Scheme 2 Sallé's Synthesis Of Ttf-based Tetrapyridine 1pmentioning

confidence: 99%

Catalytic C–H Arylation of Tetrathiafulvalenes for the Synthesis of Functional Materials

2020

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Sulfur-containing functional π-conjugated cores play key roles in materials science, mostly due to their unique electrochemical and photophysical properties. Among these, the excellent electron donor tetrathiafulvalene (TTF) has occupied a central position since the emergence of organic electronics. Peripheral C–H modification of this highly useful sulfur-containing motif has resulted in the efficient creation of new molecules that expand the applications of TTFs. This Short Review begins with the development of the palladium-catalyzed direct C–H arylation of TTF. Subsequently, it summarizes the applications of this efficient C–H transformation for the straightforward synthesis of useful TTF derivatives that are employed in a variety of research fields, demonstrating that the development of a new reaction can have a significant impact on chemical science.1 Introduction2 Development of the Palladium-Catalyzed Direct C–H Arylation of TTF3 Synthesis of TTF-Based Tetrabenzoic Acid and Tetrapyridine for MOFs4 Synthesis of TTF-Based Tetrabenzaldehyde and Tetraaniline for COFs5 Tetraarylation of TTFAQ6 Synthesis of Multistage-Redox TTF Derivatives7 Miscellaneous Examples8 Conclusions

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Dinuclear tricarbonylrhenium(i) complexes: impact of regioisomerism on the photoluminescence properties

Le Garrec,

Martins-Bessa,

Wolff

et al. 2024

Dalton Trans.

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Toward a dodecanuclear molecular Re(i) box: structural and spectroscopic properties

Cited by 3 publications

References 33 publications

Toward Heteronuclear Molecular Re(I)-Cu(II) Boxes: Structural, Luminescent, and Magnetic Properties

Toward Heteronuclear Molecular Re(I)-Cu(II) Boxes: Structural, Luminescent, and Magnetic Properties

Catalytic C–H Arylation of Tetrathiafulvalenes for the Synthesis of Functional Materials

Dinuclear tricarbonylrhenium(i) complexes: impact of regioisomerism on the photoluminescence properties

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