Quaternary Phosphorus‐Induced Iodocuprate(I)‐Based Hybrids: Water Stabilities, Tunable Luminescence and Photocurrent Responses

Abstract

Four (triphenyl)phosphonium-based quaternary phosphorus salts with different substituents (varying from methyl to n-butyl) were selected to be structural directed agents (SDAs) to construct four iodocuprate(I) hybrids via solution method, i.e., [(PPh 3 Me)(Cu 3 I 4 )] n (1), [(PPh 3 Et)(Cu 3 I 4 )] n (2), (PPh 3 iPr) 2 (Cu 2 I 4 ) (3), [(PPh 3 nBu)(Cu 3 I 4 )] n (4). The inorganic iodocuprates in 1, 2 and 4 are 1-D (Cu 3 I 4 ) n nchains constructed from Cu 5 I 11 units, but (Cu 2 I 4 ) 2in 3 is a di-nuclear cluster. Interestingly, the strength of Cu···Cu and π-π stacking interactions are weakened with the lengthening of alkyl groups on P-atom. The best water stability of 4 can be ascribed to the better hydrophobicity of n-butyl group, which deters the dispersing of [a]

<p>Multifunctional Quaternary Phosphorus/Bromoargentate Hybrids: The Achievement of Greenish Blue Luminescence, Repeatable Photocurrent Responses and Durable Antimicrobial Activities with Enhanced Water Stability</p>

“…As reported by literature, free organic quaternary phosphorus iodide (Ph 3 Pn-Bu•I) also exhibits cyan emission (at 485 nm) under excitation at 340 nm, which was attributed to the photoinduced charge transfer from the iodine anion to the phosphonium core. 15 Compared with the emission of phosphonium iodide, compound 2 with spacer length n=3 presents the largest redshift of approximately 28 nm, and conclusions could be drawn that these greenish blue emissions all stem from the photoinduced charge transfer from bromoargentates to phosphoniums. Moreover, their quantum yields are generally the same (ranging from 6.21 to 6.26%).…”

“…Comparably, the adsorption peaks of organic quaternary phosphorus salts generally appear at approximately 330 nm, corresponding to the n-π*/π-π* transitions of phenyl groups in the phosphonium core. 15 Therefore, compared with free phosphonium, the corresponding electronic transitions of 1-3 can definitely be attributed to the ligandcentered n-π*/π-π* transitions of phosphine ligands. 39 There are blanks in the range of 350-800 nm, suggesting the absence of ligand-to-ligand charge transfer (LLCT) and charge transfer between inorganic bromoargentates and organic moieties.…”

“…The stabilities of functional materials in solvents will determine their real applications. 15,38 In this work, alkylbis-(triphenyl)phosphoniums with different spacer lengths might affect their water stability. Most of the functional properties of this work were conducted in water; therefore, their stabilities in water were studied.…”

“…This phenomenon again proves the conclusion that in the quaternary phosphorus-containing hybrids, a longer alkyl chain can give rise to better water stability. 15 In addition, the thermal stability of 3 was also determined, which could not decompose until 320°C ( Figure S3). The good water/thermal stabilities will be beneficial for their long-term antibacterial performances.…”

“…[12][13][14] The hybridization of alkyl(triphenyl)phosphonium with halometallate will be a good strategy for the development of multifunctional material. 15 First, the tetrahedral geometry of alkyl(triphenyl)phosphonium cations limits benzenebenzene π−π stacking interactions in the lattice; consequently, long persistence phosphors might be achieved. Second, in alkyl(triphenyl)phosphonium/halometallate hybrids, the LUMOs were commonly localized on the phosphine ligands, while the HOMOs were occupied by halometallates.…”