Laser photolysis studies on CuI complexes of thia-calix[3]pyridine. Phosphorescence from the intramolecular charge-transfer excited state

Kinoshita, Isamu; Hamazawa, Akihisa; Nishioka, Takanori; Adachi, Haruna; Suzuki, Hiroyuki; Miyazaki, Yoshio; Tsuboyama, Akira; Okada, Shinjiro; Hoshino, Mikio

doi:10.1016/s0009-2614(03)00264-1

Cited by 10 publications

(3 citation statements)

References 29 publications

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“…Several other unconventional ligands have been utilized recently to make luminescent Cu(I) complexes such as thia-calix [3]pyridine (orange MLCT Fig. 38 The red-emitting complex [Cu(BTA)(hfac)] with BTA = bis(trimethylsilyl)acetylene and hfac = 1,1,1,5,5,5-hexa-fluoroacetyl-acetonate phosphorescence) [169], mononuclear and dinuclear azaindole-containing systems (blue LC) [170,171], heteroleptic diphosphine/diisocyanide ligands (blue MLCT) [172], pyrazolylborates (blue LC phosphorescence) [173].…”

Section: Miscellanea Of Cu(i) Luminescent Complexesmentioning

confidence: 99%

Photochemistry and Photophysics of Coordination Compounds: Copper

Armaroli

Accorsi

Cardinali

et al.

Topics in Current Chemistry

509

484

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Cu(I) complexes and clusters are the largest class of compounds of relevant photochemical and photophysical interest based on a relatively abundant metal element. Interestingly, Nature has given an essential role to copper compounds in some biological systems, relying on their kinetic lability and versatile coordination environment. Some basic properties of Cu(I) and Cu(II) such as their coordination geometries and electronic levels are compared, pointing out the limited significance of Cu(II) compounds (d 9 configuration) in terms of photophysical properties. Well-established synthetic protocols are available to build up a variety of molecular and supramolecular architectures 70 N. Armaroli et al.(e.g. catenanes, rotaxanes, knots, helices, dendrimers, cages, grids, racks, etc.) containing Cu(I)-based centers and exhibiting photo-and electroluminescence as well as light-induced intercomponent processes. By far the largest class of copper complexes investigated to date is that of Cu(I)-bisphenanthrolines ([Cu(NN) 2 ] + ) and recent progress in the rationalization of their metal-to-ligand charge-transfer (MLCT) absorption and luminescence properties are critically reviewed, pointing out the criteria by which it is now possible to successfully design highly emissive [Cu(NN) 2 ] + compounds, a rather elusive goal for a long time. To this end the development of spectroscopic techniques such as light-initiated time-resolved X-ray absorption spectroscopy (LITR-XAS) and femtosecond transient absorption have been rather fruitful since they have allowed us to firmly ground the indirect proofs of the molecular rearrangements following light absorption that had accumulated in the past 20 years. A substantial breakthrough towards highly emissive Cu(I) coordination compounds is constituted by heteroleptic Cu(I) complexes containing both N-and P-coordinating ligands ([Cu(NN)(PP)] + ) which may exhibit luminescence quantum yields close to 30% in deaerated CH 2 Cl 2 solution and have been successfully employed as active materials in OLED and LEC optoelectronic devices. Also copper clusters may exhibit luminescence bands of halide-to-metal charge transfer (XMCT) and/or cluster centered (CC) character and they are briefly reviewed along with miscellaneous Cu(I) compounds that recently appeared in the literature, which show luminescence bands ranging from the blue to the red spectral region. An Overview of Copper Historical Notes, Current Use, Consumption TrendsCopper was known to some of the oldest civilizations on record, and has a history of use that is at least 10 000 years old. A copper pendant was found in what is now northern Iraq that dates to 8700 B.C. and by 5000 B.C. there are signs of copper smelting from simple copper compounds such as malachite or azurite. This process appears to have been developed independently in several parts of the world since several centuries B.C., including Anatolia, China, Central America and West Africa. The Egyptians found that, upon addition of small amounts of tin, copper becomes easier to...

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Section: Miscellanea Of Cu(i) Luminescent Complexesmentioning

confidence: 99%

Photochemistry and Photophysics of Coordination Compounds: Copper

Armaroli

Accorsi

Cardinali

et al.

Topics in Current Chemistry

509

484

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“…Hence, thiacalixarenes show potential as highly useful molecular skeletons for porous molecular recognition materials [ 48 ]. Furthermore, a new breed of calixarene derivatives built with aromatic heterocycles, e.g., thiophene [ 49 , 50 , 51 ], dithienothiophene [ 52 ], pyridine [ 53 , 54 , 55 , 56 ], pyrimidine [ 57 ], and triazine [ 58 ], have been synthesized. These derivatives have attracted much attention due to their proper inclusiveness, electrochemical properties, and molecular geometries based on the introduction of heteroatoms.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Structure, and Characterization of Thiacalix[4]-2,8-thianthrene

2023

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Sulfur-containing macrocycles have attracted substantial interest because they exhibit unique characteristics due to their polygonal ring-shaped skeleton. In this study, a thianthrene-based cyclic tetramer with the sulfur linker, thiacalix[4]-2,8-thianthrene (TC[4]TT), was successfully prepared from a cyclo-p-phenylenesulfide derivative using acid-induced intramolecular condensation. Single crystal X-ray diffraction revealed that TC[4]TT adopts an alternative octagonal form recessed to the inner side. Its internal cavity included small solvents, such as chloroform and carbon disulfide. Due to its polygonal geometry, TC[4]TT laminated in a honeycomb-like pattern with a porous channel. Furthermore, TC[4]TT showed fluorescence and phosphorescence emission in a CH2Cl2 solution at ambient and liquid nitrogen temperatures. Both emission bands were slightly redshifted compared with those of the reference compounds (di(thanthren-2-yl)sulfane (TT2S) and thianthrene (TT)). This work describes a sulfur-containing thiacalixheterocycle-based macrocyclic system with intriguing supramolecular chemistry based on molecular tiling and photophysical properties in solution.

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“…Exciplexes are the excited state complexes and they appear as transient species in many photochemical reactions particularly photoinduced electron transfer reactions [2,[5][6][7][8]. Usually a strong binding energy in the range of 20-80 kJ/mol, charge transfer nature, relatively long lifetimes, and moderate stabilities are characteristic of exciplexes.…”

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confidence: 99%