4. Survey of Novel Multiphoton Active Materials 1257 4.1. Multiphoton Absorbing Systems 1257 4.2. Organic Molecules 1257 4.3. Organic Liquids and Liquid Crystals 1259 4.4. Conjugated Polymers 1259 4.4.1. Polydiacetylenes 1261 4.4.2. Polyphenylenevinylenes (PPVs) 1261 4.4.3. Polythiophenes 1263 4.4.4. Other Conjugated Polymers 1265 4.4.5. Dendrimers 1265 4.4.6. Hyperbranched Polymers 1267 4.5. Fullerenes 1267 4.6. Coordination and Organometallic Compounds 1271 4.6.1. Metal Dithiolenes 1271 4.6.2. Pyridine-Based Multidentate Ligands 1272 4.6.3. Other Transition-Metal Complexes 1273 4.6.4. Lanthanide Complexes 1275 4.6.5. Ferrocene Derivatives 1275 4.6.6. Alkynylruthenium Complexes 1279 4.6.7. Platinum Acetylides 1279 4.7. Porphyrins and Metallophophyrins 1279 4.8. Nanoparticles 1281 4.9. Biomolecules and Derivatives 1282 5. Nonlinear Optical Characterizations of Multiphoton Active Materials 1282

Multiphoton Absorbing Materials : Molecular Designs, Characterizations, and Applications

2.3. Ionic Liquids (ILs) 5374 2.4. Complexation Reactions on Oxidized CNTs 5375 2.5. Halogenation 5376 2.6. Cycloaddition Reactions 5377 2.7. Radical Additions 5379 2.8. Nucleophilic Additions 5381 2.9. Electrophilic Additions 5381 2.10. Electrochemical Modifications 5381 2.11. Plasma-Activation 5381 2.12. Mechanochemical Functionalizations 5382 3. Noncovalent Interactions 5382 3.1. Polynuclear Aromatic Compounds 5382 3.2. Interactions with Other Substances 5384 3.3. Interactions with Biomolecules 5385 4. Endohedral Filling 5386 4.1. Encapsulation of Fullerenes 5386 4.2. Encapsulation of Organic Substances 5387 4.3. Encapsulation of Inorganic Substances 5387 5. Decoration of CNTs with Metal Nanoparticles 5388 5.1. Covalent Linkage 5388 5.2. Direct Formation on Defect Sites 5388 5.3. Electroless Deposition 5388 5.4. Electrodeposition 5389 5.5. Chemical Decoration 5390 5.6. Deposition of Nanoparticles onto CNTs 5391 5.7. π-π Stacking and Electrostatic Interactions 5391 6. Concluding Remarks 5392 7. Acknowledgments 5392 8. References 5392

Current progress on the chemical modification of carbon nanotubes.

A Graphene Hybrid Material Covalently Functionalized with Porphyrin: Synthesis and Optical Limiting Property

A novel graphene oxide−doxorubicin hydrochloride nanohybrid (GO−DXR) was prepared via a simple noncovalent method, and the loading and release behaviors of DXR on GO were investigated. An efficient loading of DXR on GO as high as 2.35 mg/mg was obtained at the initial DXR concentration of 0.47 mg/mL. The loading and release of DXR on GO showed strong pH dependence, which may be due to the hydrogen-bonding interaction between GO and DXR. The fluorescent spectrum and electrochemical results indicate that strong π−π stacking interaction exists between them.

High-Efficiency Loading and Controlled Release of Doxorubicin Hydrochloride on Graphene Oxide

Porphyrins and phthalocyanines have outstanding chemical and thermal stability. The macrocyclic structure and chemical reactivity of tetrapyrroles offers architectural flexibility and facilitates the tailoring of chemical, physical and optoelectronic parameters. The specific optical properties of the tetrapyrrole macrocycle combined with the synthetic methodologies now available and the already available theoretical and spectroscopic knowledge on their optical behavior make porphyrins a target of choice for this area. They are versatile organic nanomaterials with a rich photochemistry and their excited state properties are easily modulated through conformational design, molecular symmetry, metal complexation, orientation and strength of the molecular dipole moment, size and degree of conjugation of the π-systems, and appropriate donor-acceptor substituents. Here we review the structural chemistry and optical properties of recently synthesized porphyrin derivatives that offer potential for nonlinear optical (NLO) applications and complement existing studies on phthalocyanines. Classes of interest include the classic A4 symmetric tetrapyrroles, while optimized systems include push-pull porphyrins, oligomeric and supramolecular self-assembled systems, films and nanoparticle systems, and highly conjugated porphyrin arrays.

Nonlinear Optical Properties of Porphyrins

Novel covalently porphyrin-functionalized single-walled carbon nanotubes (SWNTs) have been synthesized by the reaction of SWNTs with in situ generated porphyrin diazonium compounds. The resulting nanohybrid was characterized by spectroscopic (UV-Vis-NIR, FTIR and Raman) and microscopic (TEM and AFM) methods. The Raman and absorption spectroscopy data showed that the electronic properties of the modified tubes were mostly retained, without damaging their one-dimensional electronic properties. The fluorescence from the porphyrin moiety was almost completely quenched by SWNTs, indicating that the unique direct linkage mode facilitated the effective energy and electron transfer between the excited porphyrin moiety and the extended π-system of SWNTs. This novel nanohybrid material also exhibited excellent optical limiting properties.

Covalently porphyrin-functionalized single-walled carbon nanotubes: a novel photoactive and optical limiting donor–acceptor nanohybrid

DFT study on the influence of meso-phenyl substitution on the geometric, electronic structure and vibrational spectra of free base porphyrin

Nonlinear refraction and nonlinear absorption of self-assembled porphyrins in the nanosecond and picosecond regimes were studied at 532 nm by the Z-scan technique. First, a marked difference in nonlinear refraction was observed between self-assembled zinc porphyrins and free base porphyrins; however, the effects of self-assembly and metallization on nonlinear absorption are small. Second, an enhancement of nonlinear absorption was observed for the monomeric components of self-assembled structures by adding pyridine, while their nonlinear refractions remained almost unchanged as pyridine was added. It is expected that the metallization and addition of ligand can provide more convenient routes to alter the optical nonlinearities of porphyrins than the modifications of molecular structures of traditional covalent-bond organic materials.

Nonlinear absorption and nonlinear refraction of self-assembled porphyrins.

The type of donor used is found to influence greatly the optical nonlinearities of iodine charge-transfer (CT) complexes in solutions for several solvents. The magnitude and sign changes of nonlinear absorption of iodine CT complexes for different solvents as donors are observed, which implies the transition from saturable absorption to reverse saturable absorption. Compared with C60 in toluene, iodine CT complexes with toluene and benzene demonstrate larger reverse saturable absorption. Meanwhile, flexible alteration of optical nonlinearities is easily obtained by adjusting the mixture ratio of different solvents, yielding a prospective means of constructing a nonlinear medium with a large nonlinear coefficient.

Flexible alteration of optical nonlinearities of iodine charge-transfer complexes in solutions.

A general approach to construct one-dimensional face-to-face alignment of porphyrin/fullerene nanowires has been developed. This system uses extended trans-dihydroxotin(IV) porphyrin and trans-dicarboxylate-substituted [60]fullerenoacetic diacid compounds. The nanowires are arranged in regular one-dimensional linear arrays with lengths in the range 50-300 nm. In the nanowires, each fullerene unit is axially coordinated to the central metal ion of a Sn(IV) porphyrin unit via Sn-carboxylate coordination and forms a face-to-face aligned structure. The synthesis and the hierarchical structure of nanowires have been investigated. They could have potential applications for photoelectronic devices, organic solar cells and so on.

Jian-Yu Zheng

Papers

Covalently porphyrin-functionalized single-walled carbon nanotubes: a novel photoactive and optical limiting donor–acceptor nanohybrid

DFT study on the influence of meso-phenyl substitution on the geometric, electronic structure and vibrational spectra of free base porphyrin

Nonlinear absorption and nonlinear refraction of self-assembled porphyrins.

Flexible alteration of optical nonlinearities of iodine charge-transfer complexes in solutions.

Face‐to‐Face Alignment of Porphyrin/Fullerene Nanowires Linked by Axial Metal Coordination