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Boivin, Leo ; Schlachter, Adrien ; Fortin, Daniel , et al. Molecules,2023,28(23):7781. DOI: 10.3390/molecules28237781 PubMed ID: 38067511
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Abstract: The prediction of the metal cluster within a coordination polymer or complex, as well as the dimensionality of the resulting polymer or complex (i.e., 0D, 1D, 2D, or 3D), is often challenging. This is the case for Ph2P(CH2)mPPh2 ligands (1 ≤ m ≤ 8) and CuX salts, particularly for X = I. This work endeavors a systematic statistical anal. combining studies in the literature and new data, mapping the nature of the resulting CuI aggregates with eight different diphoshphines in 2:1, 3:2, 1:1, 2:3, and 1:2 CuI:Ph2P(CH2)mPPh2 molar ratios as a function of m, which lead to either pure products or mixtures Several trends are made relating stoichiometry and chain length to the CuI cluster formed (i.e., globular vs. quasi-planar). Four new X-ray structures were determined: [Cu3I2(L1)3]I, Cu3I3(L2)2, Cu2I2(L6)2, and Cu4I4(L8)2, where m is, resp., 1, 2, 6, and 8, in which the CuxIy central aggregates adopt triangular bipyramid, diamond, rhomboid, and cubane shaped motifs, resp. Photophys. measurements assisted the establishment of trends considering the paucity of the crystallog. structures. During this study, it was also found that the 0D-complex Cu2I2(Ph2P(CH2)5PPh2)2 exhibits thermally activated delayed fluorescence.
Keywords: copper(I) iodide coordination polymers ; photophysics ; TADF
Purchased from AmBeed: 1663-45-2 ; 7688-25-7 ; 2071-20-7 ; 27721-02-4 ; 19845-69-3 ; 6737-42-4 ; 4549-31-9 ; 7681-65-4 ; 41625-30-3
CAS No. : | 2071-20-7 | MDL No. : | MFCD00003537 |
Formula : | C25H22P2 | Boiling Point : | No data available |
Linear Structure Formula : | H2C(P(C6H5)2)2 | InChI Key : | XGCDBGRZEKYHNV-UHFFFAOYSA-N |
M.W : | 384.39 | Pubchem ID : | 74952 |
Synonyms : |
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Chemical Name : | Bis(diphenylphosphino)methane |
Signal Word: | Warning | Class: | |
Precautionary Statements: | P261-P305+P351+P338 | UN#: | |
Hazard Statements: | H315-H319-H335 | Packing Group: | |
GHS Pictogram: |
* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.
Yield | Reaction Conditions | Operation in experiment |
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99% | In toluene; at 80℃; for 48h;Inert atmosphere; | Dppm (3.59 g, 9.34 mmol) was dissolved in toluene (40 ml) and <strong>[4761-00-6]2-(bromomethyl)-1,3,5-trimethylbenzene</strong> (1.99 g, 9.34 mmol) was added. The reaction mixturewas heated to 80 C for two days. The resulting white precipitate of 1d was collected byfiltration, washed with toluene (2 × 20 ml) and dried in vacuum .1d. White solid, yield 99%, 5.53 g, mp 240-241 C; 1H NMR (600MHz, CDCl3): deltaH 1.68 (6H, s,o-CH3 Mes), 2.10 (3H, d, 7JHP = 2.7 Hz, p-CH3 Mes), 4.45 (2H, d, 2JHP = 13.8 Hz, P-CH2-P),4.79 (2H, d, 2JHP = 14.5 Hz, P-CH2), 6.56(2H, s, m-CH Mes), 7.18-7.23 (6H, m, CH Ph), 7.26-7.32 (4H, m, CH Ph), 7.50-7.58 (10H, m, CH Ph). 13C{H} NMR (100.6 MHz, CDCl3): deltaC 20.7(1C, d, 6JCP = 1.4 Hz, p-CH3 Mes), 21.0 (2C, d, 4JCP = 1.0 Hz, o-CH3 Mes), 22.0 (1C, dd, 1JCP =47.7 Hz, 1JCP = 32.9 Hz, P-CH2-P), 30.3 (1C, d, 1JCP = 45.4 Hz, P-CH2), 116.9 (2C, d, 1JCP = 82.6Hz, i-C Ph), 123.1 (1C, d, JCP = 9.5 Hz, C Mes), 128.9 (4C, d, JCP = 8.6 Hz, CH Ph), 129.2 (4C,d, JCP = 12.1 Hz, CH Ph), 129.5 (2C, d, 4JCP = 3.6 Hz, m-CH Mes), 129.7 (2C, s, p-CH Ph),133.4 (4C, d, JCP = 22.6 Hz, CH Ph), 134.0 (4C, dd, 2JCP = 8.9 Hz, 4JCP = 2.7 Hz, o-CH Ph),134.4 (2C, d, 4JCP= 2.9 Hz, p-CH Ph), 135.0 (2C, dd, 1JCP = 11.2 Hz, 3JCP = 8.0 Hz, i-C Ph),137.7 (1C, d, JCP = 4.4 Hz, C Mes), 137.8 (2C, d, 3JCP = 5.4 Hz, o-C Mes). 31P{H} NMR(161.9MHz, CDCl3) deltaP -23.8 (1P, d, 2JPP = 61.3 Hz), 25.8 (1P, d, 2JPP = 61.3 Hz). Anal. Calcd forC35H35P2Br (597.52): C, 70.36 H, 5.90; Br, 13.37%. Found: C, 70.20; H, 5.96; Br, 13.51%.Suitable crystals of 1d for X-ray diffraction experiments were obtained by slow diffusion of Et2Ointo a saturated solution of 1d in CHCl3. |