Toward the most versatile fluorophore: Direct functionalization of BODIPY dyes via regioselective C—H bond activation

BODIPY dyes are privileged fluorophores that are now widely used in highly diverse research fields. An overview of BODIPY dyes and a summarization of the different synthetic methodologies reported for direct C-H functionalization of the BODIPY framework have been provided.     

硫脲络合–火焰原子吸收光谱法测定低硅铝合金中的银含量

采用硫脲络合–火焰原子吸收光谱法测定低硅铝合金中的银元素含量。实验探讨了酸度及硫脲用量对银测定的影响及铝合金中基体元素与共存元素对银元素分析线的干扰情况。结果表明:选用9%的盐酸和3%的硝酸溶解试样最好,加入5 mL 50 g/L硫脲溶液可消除氯离子对试验结果的影响,基体铝元素和其它共存元素不干扰银的测定。根据低硅铝合金中银元素的含量范围,合成系列标准溶液,建立工作曲线,工作曲线的线性范围为0.05%~0.50%。银元素含量为0.30%的样品测定结果的相对标准偏差为0.15%(n=8),标准加入回收率为96.8%~98.5%。该方法操作简便、重现性好、测量结果准确可靠。     

Novel expanded porphyrinoids with multiple-inner-ring-fusion and/or tunable aromaticity

Novel expanded porphyrinoids with advanced structure features have a wide range of benefits (such as multi-metal coordination and facile tunable aromaticity) not offered by their normal porphyrin analogues. Considering research efforts have been devoted to address their limited synthetic accessibility issue. This review highlights some of these recent synthetic progresses towards these novel expanded porphyrinoids.     

Expeditious synthesis of porphyrin-cobaltacarborane conjugates

Two porphyrin-cobaltacarborane conjugates and were prepared in high yields via a nucleophilic ring-opening reaction of . These novel boron-rich and fluorescent compounds have potential application as boron delivery agents for the boron neutron capture therapy of tumors.     

Carborane functionalized pyrroles and porphyrins via the Suzuki cross-coupling reaction

A new route to carboranylated pyrroles and porphyrins is reported which involves the Suzuki coupling of readily available bromo- and boronic acid-pyrroles and bromoporphyrins with functionalized carboranes; the X-ray structures of two targeted products are presented and discussed.     

Improved synthesis of functionalized 2,2'-bipyrroles

A series of 2,2'-bipyrroles has been efficiently synthesized using an improved synthetic approach based on Pd(0)-catalyzed homocoupling of various 2-iodopyrroles. This new synthetic approach takes place at room temperature and in the presence of water. Functional groups such as formyl, ester, and nitrile are able to survive these reaction conditions. Solvents are found to play an important role in this reaction.     

Orthogonally aligned cyclic BODIPY arrays with long-lived triplet excited states as efficient heavy-atom-free photosensitizers

In photosensitizers, long triplet excited state lifetimes are key to their efficient electron transfer or energy transfer processes. Herein, we report a novel class of cyclic trimeric BODIPY arrays which were efficiently generated from easily accessible meso-mesityldipyrrinone and arylboronic acids in one pot. Arylboronic acid, for the first time, was used to provide a boron source for BODIPY derivatives. Due to the well-defined and orthogonally aligned BODIPY cores as verified by X-ray crystallography, these BODIPY arrays show strong exciton coupling effects and efficient intersystem crossings, and are novel heavy-atom-free photosensitizers with a long-lived triplet excited state (lifetime up to 257.5 μs) and good reactive oxygen species generation efficiency (up to 0.72) contributed by both ¹O₂ and O₂⁻˙ under light irradiation.

Cyclic BODIPY trimers showed strong exciton coupling in singlet excited states and long-lived triplet excited states, and generated both singlet oxygen and superoxide radicals under light irradiation, giving good reactive oxygen quantum yields and promising PDT results in vitro.     

Electropolymerizable 2,2'-Carboranyldithiophenes. Structure-Property Investigations of the Corresponding Conducting Polymer Films by Electrochemistry, UV-Visible Spectroscopy and Conducting Probe Atomic Force Microscopy

Carborane-functionalized conducting polymer films have been electrogenerated in dichloromethane from the anodic oxidation of ortho- (1), meta- (3) and para-carborane (4) isomers linked to two 2-thienyl units. The corresponding electrochemical response was characterized by a broad reversible redox system corresponding to the p-doping/undoping of the polythiophene backbone, the formal potential of which increased in the order poly(1) < poly(3) < poly(4), from ca. 0.50 to 1.15 V vs Ag/Ag(+) 10(-2) M. From further UV-visible spectroscopy analysis, the optical band gap was estimated at 1.8, 2.0 and 2.2 eV for poly(1), poly(3) and poly(4), respectively. The more conjugated and electroconductive character of poly(1) is ascribed to a more planar conformation of the conjugated backbone resulting from an intramolecular β-β' cyclization reaction in the monomer, consequently yielding a fused conjugated polymer. Molecular modeling calculations using the DFT method support this hypothesis. The surface topography and maps of the conductive domains of the electropolymerized films were evaluated by conducting probe AFM. The three polymers exhibit fairly similar morphological characteristics and a surface roughness of ~2 nm. Current-voltage (I-V) characteristics of conducting AFM tip-carborane polymer-ITO junctions showed that poly(1) had the highest conductivity.     

Synthesis of oxacalixarene-locked bisporphyrins and higher oligomers

The efficient one-step synthesis of oxacalixarene-bisporphyrins and higher oligomers from readily available starting materials is described. The X-ray structure of one oxacalix[4]arene-locked cofacial bisporphyrin, prepared in 91% yield, shows an 1,3-alternate conformation of the molecule with partial overlap of the two porphyrin rings. 1H NMR data supports a similar conformation in solution. The absorption and emission spectra of oxacalixarene-porphyrins are briefly discussed.