3.2. Thienothiophenes 1216 3.2.1. Thieno[3,4-b]thiophene Analogues 1216 3.2.2. Thieno[3,2-b]thiophene Analogues 1217 3.2.3. Thieno[2,3-b]thiophene Analogues 1218 3.3. , ′-Bridged Bithiophenes 1219 3.3.1. Dithienothiophene (DTT) Analogues 1220 3.3.2. Dithieno[3,2-b:2′3′-d]thiophene-4,4-dioxides 1221 3.3.3. Dithienosilole (DTS) Analogues 1221 3.3.4. Cyclopentadithiophene (CPDT) Analogues 1221 3.3.5. Nitrogen and Phosphor Atom Bridged Bithiophenes 1222

Functional oligothiophenes: molecular design for multidimensional nanoarchitectures and their applications.

The past decade has witnessed renewed interest and numerous unexpected discoveries in the area of main group organometallic chemistry. Unusual bonding modes have been uncovered,1-4 new materials have been developed,5,6 and new applications are being pursued.7-12 With respect to new materials with unusual properties, an exciting field is the development of hybrid polymers that combine main group elements with typical organic structures in one framework.13,14 Among main group organic-inorganic hybrid polymers, those involving Group 14 and Group 15 elements have received tremendous attention over the past several decades, with silicones, polysilanes, and polyphosphazenes among the most thoroughly studied materials.15-17 A variety of other classes of new polymers containing not only silicon and phosphorus,18-22 but also the heavier homologues, such as germanium, tin, arsenic, and antimony have been introduced more recently.23-26

Advances in the Synthesis of Organoborane Polymers for Optical, Electronic, and Sensory Applications

There is an enormous demand for chemical sensors for many areas and disciplines. High sensitivity and ease of operation are two main issues for sensor development. Fluorescence techniques can easily fulfill these requirements and therefore fluorescent-based sensors appear as one of the most promising candidates for chemical sensing. However, the development of sensors is not trivial; material science, molecular recognition and device implementation are some of the aspects that play a role in the design of sensors. The development of fluorescent sensing materials is increasingly captivating the attention of the scientists because its implementation as a truly sensory system is straightforward. This critical review shows the use of polymers, sol–gels, mesoporous materials, surfactant aggregates, quantum dots, and glass or gold surfaces, combined with different chemical approaches for the development of fluorescent sensing materials. Representative examples have been selected and they are commented here.

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Design of fluorescent materials for chemical sensing

Organophosphorus π-Conjugated Materials

Amine- and phosphine-borane adducts: new interest in old molecules.

A new family of main-chain organoborane polymeric Lewis acids (PTh−BAr) that contain Lewis acidic boron groups embedded into a polythiophene backbone has been prepared under mild conditions through tin−boron exchange reaction. When phenyl and pentafluorophenyl groups are attached to boron, blue and green luminescence is observed, respectively, while the attachment of ferrocenyl substituents leads to a characteristic red color. The incorporation of readily accessible highly Lewis acidic groups into the conjugated polymer backbone provides an opportunity for sensing of Lewis basic substrates. For instance, treatment of the polymer containing phenyl substituents on boron with pyridine leads to efficient quenching of the fluorescence, while the polymer containing ferrocenyl groups changes color from dark red to light orange.

A family of main-chain polymeric Lewis acids: synthesis and fluorescent sensing properties of boron-modified polythiophenes.

The bifunctional conjugated organoboranes Ar2B-bt-BAr2, which contain 2,2'-bithiophene (bt) linkers and different aryl substituents on boron (3: Ar = p-tBuC6H4; 4: Ar = C6F5; 5: Ar = C6F5, Fc; Fc = ferrocenyl), have been synthesized. The electronic communication between the boron centers and cooperativity effects in the binding of pyridine have been investigated by a comprehensive study using X-ray crystallography, DFT calculations, cyclic voltammetry, 1H and 19F NMR, and UV visible absorption and emission spectroscopy. A comparison of the single-crystal X-ray structures of 4 and 4Py2 revealed a strongly diminished bond alternation in the thiophene rings for 4, indicative of a high degree of electronic delocalization. DFT calculations are in good agreement with the structural features determined from the X-ray analysis and, consistent with the experimental absorption and emission data, predict a smaller HOMO-LUMO gap for green luminescent 4 in comparison to blue luminescent 3. The complexation of pyridine to the two boron centers was further investigated by 1H and 19F NMR for 4 and by 1H NMR and UV-visible absorption spectroscopy for 3. We found that binding of the first pyridine molecule to one of the boryl groups significantly lowers the Lewis acidity of the other boryl group. For 3, the interaction parameter a, which provides a measure of communication between the boron sites, was determined to be a = 0.23 by UV-visible titration and 0.21 by 1H NMR spectroscopy. Further enhanced electronic communication was observed for the more highly Lewis acidic fluorinated derivative 4, for which a = 0.025 according to 19F and 1H NMR spectroscopy.

Maria Victor

Papers

A family of main-chain polymeric Lewis acids: synthesis and fluorescent sensing properties of boron-modified polythiophenes.

Electronic communication and negative binding cooperativity in diborylated bithiophenes.

Luminescent main chain organoboron modified polythiophenes as sensing materials