Luminescence enhancement and tuning via multiple cooperative supramolecular interactions in an ion-paired multinuclear complex

Yang, Chi; Elbjeirami, Oussama; Gamage, Chammi S. Palehepitiya; Dias, H. V. Rasika; Omary, Mohammad A.

doi:10.1039/c1cc11161b

Cited by 49 publications

(39 citation statements)

References 21 publications

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“…[311] Even in the ten-membered rings formed upon 1:1 complexation of AgBF 4 or AgOSO 2 CF 3 with an "N-confused" bis-porphyrin (having one "extrovert" N atom in each carbaporphyrinoid) the perpendicular arrangement of the bis-porphyrins leads to an Ag-Ag contact of only 3.107(2) . [312] Ten-membered rings with short transannular contacts (average 3.0 ) were also found in the silver complexes of Schiff bases derived from ethylenediamine owing to the folding of the metallocycle (96). [313] Dimetallacycles with the same ring size were again discovered with the oxime tautomer of N 6 -methoxyadenine (97 a).…”

Section: Double Support By No-and Ns-coordinating Ligandsmentioning

confidence: 95%

“…[95] Like these compounds, silver(I) 3,5-bis(trifluoromethyl)pyrazolate also shows an extensive network of Ag-Ag contacts with other ligands (Section 2.5.3). [96]…”

Section: Thermal Contraction and Negative Linear Compressibilitymentioning

confidence: 99%

“…The results have been explained by a loosening of the Ag-Ag contacts by solvation at high dilution in the solvent, and their tightening at low temperature in the crystal. [96] 3. Selected Modes of Argentophilic Interactions…”

Section: Photoluminescencementioning

confidence: 99%

“…[348] The aromatic hydrocarbons become inserted between the stacked metallacycles leading to modified UV/ Vis absorption and emission properties, observed, for example, in the vapochromic behavior of the luminescent crystals of these compounds. [96,[342][343][344][345][346][347][349][350][351] The different results obtained from crystals and solutions of the compounds have suggested that the inter-trimer contacts are the origin of the photochromic effects in most cases. The majority of pertinent studies focused on gold compounds of this type, with the silver analogues being complementary.…”

Section: Double Support By No-and Ns-coordinating Ligandsmentioning

confidence: 99%

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Argentophilic Interactions

2014

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The decade 1990-2000 saw a growing interest in aurophilic interactions in gold chemistry. These interactions were found to influence significantly a variety of structural and other physical characteristics of gold(I) compounds. The attention paid to this unusual and counterintuitive type of intra- and intermolecular bonding between seemingly closed-shell metal centers has rapidly been extended to also include silver chemistry. Hundreds of experimental and computational studies have since been dedicated to the argentophilicity phenomenon. The results of this development are reviewed herein focusing on molecular systems where two or more silver(I) centers are in close contact leading to specific structural characteristics and a variety of novel physical properties. These include strongly modified ligand-to-metal charge-transfer processes observed in absorption and emission spectroscopy, but also colossal positive and negative thermal expansion on the one hand and unprecedented negative linear compressibility of crystal parameters on the other.

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Section: Double Support By No-and Ns-coordinating Ligandsmentioning

confidence: 95%

“…[95] Like these compounds, silver(I) 3,5-bis(trifluoromethyl)pyrazolate also shows an extensive network of Ag-Ag contacts with other ligands (Section 2.5.3). [96]…”

Section: Thermal Contraction and Negative Linear Compressibilitymentioning

confidence: 99%

Section: Photoluminescencementioning

confidence: 99%

Section: Double Support By No-and Ns-coordinating Ligandsmentioning

confidence: 99%

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Argentophilic Interactions

2014

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“…With regard to the previous summary about the luminescence studies of silver clusters, the emission band is tentatively assigned to a ligand‐to‐metal charge‐transfer (S 2− →Ag) parentage with a Ag 9 cluster‐centered triplet excited states that is modified by argentophilic interactions although a mixing of a S‐ or P‐based ligand‐centered character cannot be completely excluded. A blue‐shifted emission upon cooling is not common because of the well‐known shrinkage of Ag⋅⋅⋅Ag contacts at low temperature, which can narrow the energy gap of metal‐centered phosphorescence to a certain extent, causing the common bathochromic emission, as seen in many other silver cluster . This hypsochromic‐shifted emission behavior is probably a result of the significantly restricted rotation of the peripheral phenyl ring and the t Bu groups at low temperature, which overwhelms the excitation percentage occupied by Ag⋅⋅⋅Ag interactions.…”

Section: Resultsmentioning

confidence: 99%

General Assembly of Twisted Trigonal‐Prismatic Nonanuclear Silver(I) Clusters

Zhou

et al. 2016

Chemistry A European J

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A general class of C3 -symmetric Ag9 clusters, [Ag9 S(tBuC6 H4 S)6 (dpph)3 (CF3 SO3 )] (1), [Ag9 (tBuC6 H4 S)6 (dpph)3 (CF3 SO3 )2 ]⋅CF3 SO3 (2), [Ag9 (tBuC6 H4 S)6 (dpph)3 (NO3 )2 ] ⋅NO3 (3), and [Ag9 (tBuC6 H4 S)7 (dpph)3 (Mo2 O7 )0.5 ]2 ⋅2 CF3 COO (4) (dpph=1,6-bis(diphenylphosphino)hexane), with a twisted trigonal-prism geometry was isolated by the reaction of polymeric {(HNEt3 )2 [Ag10 (tBuC6 H4 S)12 ]}n , 1,6-bis(diphenylphosphino)hexane, and various silver salts under solvothermal conditions. The structures consist of discrete clusters constructed from a girdling Ag9 twisted trigonal prism with the top and bottom trigonal faces capped by diverse anions (i.e., S(2-) and CF3 SO3 (-) for compound 1, 2×CF3 SO3 (-) for compound 2, 2×NO3 (-) for compound 3, and tBuC6 H4 S(-) and Mo2 O7 (2-) for compound 4). This trigonal prism is bisected by another shrunken Ag3 trigon at its waist position. Interestingly, two inversion-related Ag9 trigonal-prismatic clusters are dimerized by the Mo2 O7 (2-) ion in compound 4. The twist is amplified by the bulkier thiolate, which also introduces high steric-hindrance for the capping ligand, that is, the longer dpph ligand. Four more silver-sulfur clusters (namely, compounds 5-8) with their nuclearity ranging from 6-10 were solely characterized by single-crystal X-ray diffraction to verify the above-described synergetic effect of mixed ligands in the construction of Ag9 twisted trigonal prisms. Surprisingly, only cluster 1 emits yellow luminescence at λ=584 nm at room temperature, which may be attributed to a charge transfer from the S 3p orbital to the Ag 5s orbital, or mixed with metal-centered (MC) d(10) →d(9) s(1) transitions. Upon cooling from 300 to 80 K, the emission intensity was enhanced along with a hypsochromic shift. The good linear relationship between the maximum emission intensity and the temperature for compound 1 in the range of 180-300 K indicates that this is a promising molecular luminescent thermometer. Furthermore, cyclic voltammetric studies indicated that the diffusion- and surface-controlled redox processes were determined for compounds 1 and 3 as well as compound 4, respectively.

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Thermally Activated Delayed Fluorescent Ag(I) Complexes for Highly Efficient Scintillation and High‐Resolution X‐Ray Imaging

Yuan,

Zhang,

Chen

et al. 2024

Adv Funct Materials

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Organic thermally activated delayed fluorescent (TADF) scintillators hold promising potential for applications in medical radiography and security detection, but the poor X‐ray absorption ability and inferior radioluminescence (RL) hampered their progression. Herein, the study has pioneered the development of high‐performance TADF Ag(I)‐based scintillators from M2X2(dppb)2 (M = Ag, Cu; X = Cl, Br, I) complexes with 1,2‐Bis(diphenylphosphino)benzene (dppb) ligand. In comparison with Cu(I) complexes, the Ag(I) series generally exhibited superior scintillation performance. Notably, Ag2Cl2(dppb)2 (Ag1) stands out with exceptionally high RL intensity (≈125% higher than that of CsI:Tl) and a low detection limit of 59.8 nGy s−1. The outstanding scintillation performance of Ag1 is primarily attributed to the synergistic effect of the high exciton utilization efficiency origin from a small singlet‐triplet energy gap, enhanced X‐ray absorption capacity by heavy atoms, and the high photoluminescence quantum yield (76.47% in ambient atmosphere). By fabricating a flexible film constructed with Ag1 submicron crystalline powders, a high spatial resolution of 25.0 lp mm−1 for X‐ray imaging is obtained. It offers new opportunities for utilizing TADF metal–organic complexes for highly efficient X‐ray scintillation and imaging.

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Luminescence enhancement and tuning via multiple cooperative supramolecular interactions in an ion-paired multinuclear complex

Cited by 49 publications

References 21 publications

Argentophilic Interactions

Argentophilic Interactions

General Assembly of Twisted Trigonal‐Prismatic Nonanuclear Silver(I) Clusters

Thermally Activated Delayed Fluorescent Ag(I) Complexes for Highly Efficient Scintillation and High‐Resolution X‐Ray Imaging

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