Synthesis, Crystal Structure, Photophysical Properties, and DFT Calculations of a Bis(tetrathia-calix[4]arene) Tetracadmium Complex

Fu, Ming‐Lai; Rangel, Norma L.; Adams, Richard D.; Seminario, Jorge M.

doi:10.1007/s10876-010-0347-1

Cited by 16 publications

(18 citation statements)

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“…The frameworks of calix[n]arenes ligands are flexible and calix [4]arenes are the most widely used ones. The original calix [4]arenes contain four phenol groups connected by four methyl groups. In most cases, they behave as tetradentate ligands, bonding to one or more metal ions via phenolic oxygen atoms.…”

Section: ) Synthesis Crystal Structure Photophysical Properties Amentioning

confidence: 99%

“…Their ability to coordinate metal ions can be enhanced by introduction of heteroatoms to the parent calixarenes. Usually the upper and lower rim positions of the calix [4]arenes are modified with groups such as alcohols and amines. In addition, it has been shown that the methylene units can be replaced by dimethylsilyl groups, sulfur, sulfoxide and sulfone.…”

Section: ) Synthesis Crystal Structure Photophysical Properties Amentioning

confidence: 99%

“…Thiacalix [4]arenes have a unique ability to serve as polydentate, metal-assembling ligands, because they can coordinate to metal atoms and ions by using both their four soft sulfur atoms and their four hard phenolic oxygen atoms. p-tert-Butylthiacalix [4]arene (H 4 tca) was first used for applications in solvent extraction with first-row transition metal ions.…”

Section: ) Synthesis Crystal Structure Photophysical Properties Amentioning

confidence: 99%

“…p-tert-Butylthiacalix [4]arene (H 4 tca) was first used for applications in solvent extraction with first-row transition metal ions. Thiacalixarene was also used successfully for the concentration and separation of heavy metal ions.…”

Section: ) Synthesis Crystal Structure Photophysical Properties Amentioning

confidence: 99%

“…CdS and CdSe quantum dots have attracted attention as light harvesting agents for use in photovoltaic devices. We have now synthesized and studied the structure and photophysical properties of the new bis(tert-Butylthiacalix [4]arene)tetracadmium (II) complex, Cd 4 (tca) 2 , 3. Compound 3 was obtained in 66% yield from the reaction of cadmium acetate with deprotonated H 4 tca in 1:2 ratio in DMF/CH 3 CH 2 OH mixture solvent at reflux.…”

Section: ) Synthesis Crystal Structure Photophysical Properties Amentioning

confidence: 99%

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Technical Report

Adams¹

2011

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Executive SummaryCadmium selenide nanoparticles and nanoclusters were prepared and added to polymer solar cells to improve their photon capture ability. These nanoparticles did exhibit some beneficial effects on the photon conversion efficiencies of selected polymer solar cells. Ternary bulk heterojunction systems based on composites of methyl viologen-doped, CdSe nanoparticles blended with poly (3-hexothiopene) (P3HT) and 6, 6-phenyl C 61 -butyric acid methyl ester (PCBM) were also tested. It was found that the devices with methyl viologen-doped CdSe nanoparticles do produce more photocurrent in a region surrounding the absorption peak of the particles (560 to 660nm) when compared to pristine P3HT:PCBM devices. Gold nanorods were also prepared and tested in some solar cells. These nanorods did produce a very small enhancement in photon absorbance, but the observed increase the photon conversion efficiency was not sufficient to make the effort worthwhile. Comparison of Accomplishments with Goals and Objectives of the project.Our goals were (1) to prepare cadmium sulfide and cadmium selenide clusters and nanoparticles to be tested as photon absorbers to enhance the photon conversion efficiency of polymer solar polymer solar cells and (2) to prepare gold and silver nanorods to be added to polymer solar cells to enhance their photon capture capability. The cadmium sulfide and cadmium selenide nanoparticles and some new nanoclusters were prepared. The cadmium selenide nanoparticles were also tested in solar cells and did exhibit some positive effects when they were combined with certain co-absorbing polymers. Due to solubility problems that were not solved in the available time, the new nanoclusters were not tested in solar cells. Ternary bulk heterojunction systems based on composites of methyl viologen doped, CdSe nanoparticles blended with poly (3-hexothiopene) (P3HT) and 6, 6-phenyl C 61 -butyric acid methyl ester (PCBM) have been examined in detail. The methyl viologen was added to promote charge separation of the initially formed excitons. It was found that the devices with CdSe produce more photocurrent in a region surrounding the absorption peak of the particles (560 to 660nm) when compared to a pristine P3HT:PCBM device. Gold nanorods were prepared and tested in some solar cells. These did show a very small enhancement in photon absorbance. However, the increase in short circuit current was negligible, which suggests that this antenna effect produces no significant increase in photocurrent generation. Efforts to synthesize niobium-doped zinc oxide nanoparticles for use in polymer solar polymer solar cells were also made. The nanoparticles were prepared, but they were not tested in the cells before the termination of the funding of the project. Summary of Project

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Section: ) Synthesis Crystal Structure Photophysical Properties Amentioning

confidence: 99%

Section: ) Synthesis Crystal Structure Photophysical Properties Amentioning

confidence: 99%

Section: ) Synthesis Crystal Structure Photophysical Properties Amentioning

confidence: 99%

Section: ) Synthesis Crystal Structure Photophysical Properties Amentioning

confidence: 99%

Section: ) Synthesis Crystal Structure Photophysical Properties Amentioning

confidence: 99%

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Technical Report

Adams¹

2011

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Coordination Chemistry and Applications of Phenolic Thiacalixarene–Metal Complexes

Cragg

Marcos

2017

Patai's Chemistry of Functional Groups

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Thiacalixarenes are members of the calixarene family in which sulfur has replaced one or more of the methylene bridges between the phenolic moieties of the macrocycles. Oxidation of the thiacalixarenes leads to sulfinyl and sulfonyl homologs. The incorporation of sulfur affects the metal‐binding affinities of these calixarenes over their all‐carbon analogs through the abilities of the heteroatoms both to bind directly and to influence lower rim phenolic binding. Other binding motifs are possible for the oxidized thiacalixarenes leading to a vast array of complexes with metal cations. This chapter covers the literature concerning thiacalixarenes containing free OH groups at the lower rim since they were first reported. Their coordination chemistry toward alkali, alkaline earth, transition, heavy, lanthanide, and actinide metals is discussed. Examples of crystal structures of these metal complexes are given, as well as brief descriptions of their applications in fields such as catalysis, transition‐metal extraction, and cation transport.

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Spectroscopic and Photophysical Studies of Charge‐Transfer in a Cd₈ Thiolate Cluster Complex Containing a Coordinated N‐Methyl‐4,4′‐bipyridinium Ligand

Adams

Cristancho

et al. 2010

Eur J Inorg Chem

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Synthesis, Crystal Structure, Photophysical Properties, and DFT Calculations of a Bis(tetrathia-calix[4]arene) Tetracadmium Complex

Cited by 16 publications

References 40 publications

Technical Report

Technical Report

Coordination Chemistry and Applications of Phenolic Thiacalixarene–Metal Complexes

Spectroscopic and Photophysical Studies of Charge‐Transfer in a Cd₈ Thiolate Cluster Complex Containing a Coordinated N‐Methyl‐4,4′‐bipyridinium Ligand

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Synthesis, Crystal Structure, Photophysical Properties, and DFT Calculations of a Bis(tetrathia-calix[4]arene) Tetracadmium Complex

Cited by 16 publications

References 40 publications

Technical Report

Technical Report

Coordination Chemistry and Applications of Phenolic Thiacalixarene–Metal Complexes

Spectroscopic and Photophysical Studies of Charge‐Transfer in a Cd8 Thiolate Cluster Complex Containing a Coordinated N‐Methyl‐4,4′‐bipyridinium Ligand

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Spectroscopic and Photophysical Studies of Charge‐Transfer in a Cd₈ Thiolate Cluster Complex Containing a Coordinated N‐Methyl‐4,4′‐bipyridinium Ligand