Platinum(II) Complexes Bearing 2‐(9,9‐Dihexadecyl‐7‐R‐fluoren‐2‐yl)‐1,10‐phenanthroline Ligands: Synthesis, Photophysics and Reverse Saturable Absorption

Liu, Xuguang; Sun, Wenfang

doi:10.1002/ejic.201300466

Cited by 5 publications

(5 citation statements)

References 69 publications

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“…430 nm (450 nm for 1) and a broad tail from 440 nm (450 nm for 1) to 500 nm. Comparing to the UV-vis absorption spectra of their respective ligands and with reference to the other Pt(II) C^N^N chloride complexes with similar structures, 29 the major absorption bands can be attributed to predominantly the ligand centered 1 π,π* transitions; while the broad tail is believed to be dominated by the 1 MLCT transition, probably mixed with some intraligand charge transfer (from the ethynylfluorene component to the bipyridine component) characters. The 1 π,π* transitions in the complexes are significantly red-shifted compared to those in their respective ligands, indicating the electron delocalization induced by the interactions with the metal ion.…”

Section: Papermentioning

confidence: 87%

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Synthesis, photophysics, and reverse saturable absorption of platinum complexes bearing extended π-conjugated C^N^N ligands

Sun

2013

Dalton Trans.

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The synthesis of ligands 1-L-6-L that feature the 6-[9,9-di(2-ethylhexyl)-7-R-9H-fluoren-2-yl]-2,2'-bipyridine (C^N^N) core (R = 4-R'-phenylethynyl with R' = NO2, benzothiazol-2-yl (BTZ), H and OCH3 or R = 4'-BTZ-phenyl or BTZ) and their platinum complexes 1-6 were reported in this paper. The photophysical properties of these ligands and the Pt(II) complexes, including the UV-vis absorption spectra, emission characteristics at room temperature and at 77 K, and the triplet transient difference absorption spectra, were systematically investigated in order to understand the effects of the substituent at the 4-position of the 1-ethynylphenyl component and the extension of π-conjugation between the C^N^N core and the BTZ substituent. Reverse saturable absorption (RSA) of complexes 1-6 was demonstrated at 532 nm using 4.1 ns laser pulses. The UV-vis absorption spectra of 1-L-6-L are featured by strong (1)π,π* transitions in the blue spectral region, and the absorption bands are effectively red-shifted by substitution at the 4-position of the ethynylphenyl motif and by the extended π-conjugation of the linkage. A similar effect was observed for the fluorescence spectra of these ligands in CH2Cl2 at room temperature, but the nature of the fluorescence varies from (1)π,π* fluorescence in 3-L and 6-L, to intraligand charge transfer ((1)ILCT) fluorescence in 1-L, 2-L and 5-L; while 4-L possesses mixed (1)π,π*/(1)ILCT characters. All ligands exhibit moderate triplet transient absorption (TA) in the visible spectral region, with substitution at the 4-position of the ethynylphenyl component broadening of the TA bands, while extended π-conjugation of the linkage inducing red-shifts of the TA bands. For Pt(II) complexes 1-6, their UV-vis absorption spectra constitute red-shifted (1)π,π* transitions and low-energy metal-to-ligand charge transfer ((1)MLCT/(1)ILCT) tails. The emission of these complexes at room temperature in CH2Cl2 predominantly originates from the C^N^N core localized (3)π,π* state, probably mixed with minor (3)MLCT character. 4-Position substitution and extended π-conjugation on the ligands exert a negligible effect on the shape and energy of the emission spectra. Similar to their respective ligands, 1-6 all exhibit broader and red-shifted TA spectra with respect to their ligands and both the 4-position substitution and extended π-conjugation bathochromically shift the TA band maxima. The nonlinear transmission experiments carried out for 1-6 at 532 nm reveal that all complexes exhibit strong reverse saturable absorption (RSA), and the degree of RSA follows this trend: 6 <4 <5 <2 ≤3 <1. The RSA performance is efficiently improved by electron-withdrawing substituents (NO2 and BTZ) and by extending the π-conjugation; while electron-donating substituent (OCH3 in 4) decreases the RSA at 532 nm.

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Section: Papermentioning

confidence: 87%

“…This phenomenon is also consistent with that observed from the Pt(II) complexes with a 2-(9,9-dihexadecyl-7-(4-R-phenylethynyl)-fluoren-2-yl)-1,10-phenanthroline ligand. 29 A concentration-dependent emission study of 1-6 in CH 2 Cl 2 was conducted. As exemplified in Fig.…”

Section: Dalton Transactions Papermentioning

confidence: 99%

Synthesis, photophysics, and reverse saturable absorption of platinum complexes bearing extended π-conjugated C^N^N ligands

Sun

2013

Dalton Trans.

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“…Scheme 13. Povarov Reaction Developed by Shibata et al 255,256 Liu et al 303,304 developed platinum(II) complexes based on fluorenyl-derived phen (Scheme 31) in order to increase the πdonating ability of the aryl ring to improve the non-linear absorption properties of the corresponding complexes.…”

Section: Friedlandler Reactionmentioning

confidence: 99%

“…Thummel and his group have applied this reaction to obtain various phen sub derivatives that can be further on coordinated with various metal ions. The authors have studied their photophysical properties − and more recently the application of cobalt complexes as catalysts for proton reduction into H 2 under visible light. , Other groups have also used this condensation for the formation of various phen sub derivatives. ,,− This reaction has been widely employed; thus, in the following, only selected examples will be presented.…”

Section: Convergent Synthetic Pathwaysmentioning

confidence: 99%

Fifty Shades of Phenanthroline: Synthesis Strategies to Functionalize 1,10-Phenanthroline in All Positions

Queffélec,

Pati,

Pellegrin

2024

Chem. Rev.

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1,10-Phenanthroline (phen) is one of the most popular ligands ever used in coordination chemistry due to its strong affinity for a wide range of metals with various oxidation states. Its polyaromatic structure provides robustness and rigidity, leading to intriguing features in numerous fields (luminescent coordination scaffolds, catalysis, supramolecular chemistry, sensors, theranostics, etc.). Importantly, phen offers eight distinct positions for functional groups to be attached, showcasing remarkable versatility for such a simple ligand. As a result, phen has become a landmark molecule for coordination chemists, serving as a must-use ligand and a versatile platform for designing polyfunctional arrays. The extensive use of substituted phenanthroline ligands with different metal ions has resulted in a diverse array of complexes tailored for numerous applications. For instance, these complexes have been utilized as sensitizers in dye-sensitized solar cells, as luminescent probes modified with antibodies for biomaterials, and in the creation of elegant supramolecular architectures like rotaxanes and catenanes, exemplified by Sauvage’s Nobel Prize-winning work in 2016. In summary, phen has found applications in almost every facet of chemistry. An intriguing aspect of phen is the specific reactivity of each pair of carbon atoms ([2,9], [3,8], [4,7], and [5,6]), enabling the functionalization of each pair with different groups and leading to polyfunctional arrays. Furthermore, it is possible to differentiate each position in these pairs, resulting in non-symmetrical systems with tremendous versatility. In this Review, the authors aim to compile and categorize existing synthetic strategies for the stepwise polyfunctionalization of phen in various positions. This comprehensive toolbox will aid coordination chemists in designing virtually any polyfunctional ligand. The survey will encompass seminal work from the 1950s to the present day. The scope of the Review will be limited to 1,10-phenanthroline, excluding ligands with more intracyclic heteroatoms or fused aromatic cycles. Overall, the primary goal of this Review is to highlight both old and recent synthetic strategies that find applicability in the mentioned applications. By doing so, the authors hope to establish a first reference for phenanthroline synthesis, covering all possible positions on the backbone, and hope to inspire all concerned chemists to devise new strategies that have not yet been explored.

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“…This step was carried out according to a protocol described by Sun. 23 n-BuLi (9.38 mL, 1.6 M in hexanes, 15.0 mmol) was added dropwise to a magnetically stirred solution of benzothiazole (1.35 g, 10.0 mmol) in THF (40 mL) maintained under an atmosphere of argon at −78 °C. After 1 h, Bu 3 SnCl (3.26 g, 10.0 mmol) was added dropwise and the ensuing reaction mixture was gradually warmed to room temperature over 4 h. The reaction mixture was then concentrated under reduced pressure.…”

Section: ■ Introductionmentioning

confidence: 99%

Cationic Charge-Appended Abnormal Carbenes: Synthesis and Study of Electronically Modified Abnormal N-Heterocyclic Carbenes

et al. 2021

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A range of palladium complexes featuring electronically modified, imidazole-based abnormal N-heterocyclic carbene (aNHC) ligands have been prepared in the hopes of accessing a new class of cationic aNHC ligands electronically distinct from normal NHCs and aNHCs. These palladium complexes represent the first examples of transition metal-ligated aNHC complexes featuring a cationic moiety adjacent to the abnormal carbene center. It was anticipated that these design principles could facilitate electron transfer between the imidazolinylidene and the cationic heterocycle, thus reducing the electron density at the abnormal carbene center. However, this case study suggests that greater conformational restrictions that allow for heterocycle coplanarity are necessary to achieve significant electron transfer and enable access to a new class of cationic charge-appended aNHCs with unique electronic properties.

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Platinum(II) Complexes Bearing 2‐(9,9‐Dihexadecyl‐7‐R‐fluoren‐2‐yl)‐1,10‐phenanthroline Ligands: Synthesis, Photophysics and Reverse Saturable Absorption

Cited by 5 publications

References 69 publications

Synthesis, photophysics, and reverse saturable absorption of platinum complexes bearing extended π-conjugated C^N^N ligands

Synthesis, photophysics, and reverse saturable absorption of platinum complexes bearing extended π-conjugated C^N^N ligands

Fifty Shades of Phenanthroline: Synthesis Strategies to Functionalize 1,10-Phenanthroline in All Positions

Cationic Charge-Appended Abnormal Carbenes: Synthesis and Study of Electronically Modified Abnormal N-Heterocyclic Carbenes

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