Synthesis,Structural Characterization,Photophysics, and Broadband Nonlinear Absorption of a Platinum(II) Complex with the 6‐(7‐Benzothiazol‐2′‐yl‐9,9‐diethyl‐9 H‐fluoren‐2‐yl)‐2,2′‐bipyridinyl Ligand

A platinum complex with the 6‐(7‐benzothiazol‐2′‐yl‐9,9‐diethyl‐9H‐fluoren‐2‐yl)‐2,2′‐bipyridinyl ligand ( 1 ) was synthesized and the crystal structure was determined. UV/Vis absorption, emission, and transient difference absorption of 1 were systematically investigated. DFT calculations were carried out on 1 to characterize the electronic ground state and aid in the understanding of the nature of low‐lying excited electronic states. Complex 1 exhibits intense structured ¹π–π* absorption at λ_abs<440 nm, and a broad, moderate ¹M LCT/¹LLCT transition at 440–520 nm in CH₂Cl₂ solution. A structured ³π–π*/³M LCT emission at about 590 nm was observed at room temperature and at 77 K. Complex 1 exhibits both singlet and triplet excited‐state absorption from 450 nm to 750 nm, which are tentatively attributed to the ¹π–π* and ³π–π* excited states of the 6‐(7‐benzothiazol‐2′‐yl‐9,9‐diethyl‐9H‐fluoren‐2‐yl)‐2,2′‐bipyridine ligand, respectively. Z‐scan experiments were conducted by using ns and ps pulses at 532 nm, and ps pulses at a variety of visible and near‐IR wavelengths. The experimental data were fitted by a five‐level model by using the excited‐state parameters obtained from the photophysical study to deduce the effective singlet and triplet excited‐state absorption cross sections in the visible spectral region and the effective two‐photon absorption cross sections in the near‐IR region. Our results demonstrate that 1 possesses large ratios of excited‐state absorption cross sections relative to that of the ground‐state in the visible spectral region; this results in a remarkable degree of reverse saturable absorption from 1 in CH₂Cl₂ solution illuminated by ns laser pulses at 532 nm. The two‐photon absorption cross sections in the near‐IR region for 1 are among the largest values reported for platinum complexes. Therefore, 1 is an excellent, broadband, nonlinear absorbing material that exhibits strong reverse saturable absorption in the visible spectral region and large two‐photon‐assisted excited‐state absorption in the near‐IR region.     

One- and two-photon photochemistry and photophysics of poly(arylenevinylene)s containing a biphenyl moiety.

Photochemical and photophysical properties were investigated for poly(arylenevinylene)s containing a flexible biphenyl "hinge" unit by applying one-photon (OP) and two-photon (TP) excitation to explore excited-state properties. The poly(arylenevinylene)s were poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(4,4'-dihexyloxy-3,3'-biphenylenevinylene)] (1), poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(2,2'-dihexyloxy-3,3'-biphenylenevinylene)] (2), and poly[(2,5-dihexyloxy-p-phenylenevinylene)-alt-(2,2'-biphenylenevinylene)] (3). Effective emission quantum yields and related photonic properties were evaluated on a realistic per-chromophore basis using effective conjugation lengths based on the Strickler-Berg relationship. Intramolecular photocyclization was deduced to occur in the one case where the biphenyl molecular connectivity permitted the reaction, based on matrix-assisted laser desorption/ionization time-of-flight (MALDI-TOF), heteronuclear multiple-quantum coherence (HMQC)-NMR, and gel-permeation chromatography (GPC) results. The various photoprocesses could be induced by either OP or TP excitation, though the first excited singlet state is the photoactive state. The higher excitation energy of the TP excited state favors indirect population of the S, state by electronic coupling between the TP and OP excited states [lambda(max)TPE (nm): 726; delta (GM): 1=229, 2=215, 3= 109). Photochemical processes occurring from the lowest OP excited state (S1) could therefore also be indirectly induced by TP excitation.     

Electronic and vibronic contributions to two-photon absorption in donor-acceptor-donor squaraine chromophores

Many squaraines have been observed to exhibit two-photon absorption at transition energies close to those of the lowest energy one-photon electronic transitions. Here, the electronic and vibronic contributions to these low-energy two-photon absorptions are elucidated by performing correlated quantum-chemical calculations on model chromophores that differ in their terminal donor groups (diarylaminothienyl, indolenylidenemethyl, dimethylaminopolyenyl, or 4-(dimethylamino)phenylpolyenyl). For squaraines with diarylaminothienyl and dimethylaminopolyenyl donors and for the longer examples of 4-(dimethylamino)phenylpolyenyl donors, the calculated energies of the lowest two-photon active states approach those of the lowest energy one-photon active (1B(u)) states. This is consistent with the existence of purely electronic channels for low-energy two-photon absorption (TPA) in these types of chromophores. On the other hand, for all squaraines containing indolinylidenemethyl donors, the calculations indicate that there are no low-lying electronic states of appropriate symmetry for TPA. Actually, we find that the lowest energy TPA transitions can be explained through coupling of the one-photon absorption (OPA) active 1B(u) state with b(u) vibrational modes. Through implementation of Herzberg-Teller theory, we are able to identify the vibrational modes responsible for the low-energy TPA peak and to reproduce, at least qualitatively, the experimental TPA spectra of several squaraines of this type.     

Synthesis, fluorescence, and two-photon absorption of a series of elongated rodlike and banana-shaped quadrupolar fluorophores: a comprehensive study of structure-property relationships

An extensive series of push-push and pull-pull derivatives was prepared from the symmetrical functionalization of an ambivalent core with conjugated rods made from arylene-vinylene or arylene-ethynylene building blocks, bearing different acceptor or donor end-groups. Their absorption and photoluminescence, as well as their two-photon-absorption (TPA) properties in the near infrared (NIR) region, were systematically investigated to derive structure-property relationships and to lay the guidelines for both spectral tuning and amplification of molecular TPA in the target region. Whatever the nature of the core or of the connectors, push-push systems were found to be more efficient than pull-pull systems, and planarization of the core (fluorene versus biphenyl) always leads to an increase in the TPA cross sections. In contrast, increasing the conjugation length as well as replacement of a phenylene moiety by a thienylene moiety in the conjugated rods did not necessarily lead to increased TPA responses. The present study also demonstrated that the topology of the conjugated rods can dramatically influence the TPA properties. This is of particular interest in terms of molecular engineering for specific applications, as both TPA properties and photoluminescence characteristics can be considerably affected. Thus, it becomes possible to optimize the transparency/TPA and fluorescence/TPA efficiency trade-offs for optical limiting in the red-NIR region (700-900 nm) and for two-photon-excited fluorescence (TPEF) microscopy applications, respectively.     

Ruthenium(II) complexes with improved photophysical properties based on planar 4'-(2-pyrimidinyl)-2,2':6',2' '-terpyridine ligands

A series of new tridentate polypyridine ligands, made of terpyridine chelating subunits connected to various substituted 2-pyrimidinyl groups, and their homoleptic and heteroleptic Ru(II) complexes have been prepared and characterized. The new metal complexes have general formulas [(R-pm-tpy)Ru(tpy)]2+ and [Ru(tpy-pm-R)2]2+ (tpy = 2,2':6',2' '-terpyridine; R-pm-tpy = 4'-(2-pyrimidinyl)-2,2':6',2' '-terpyridine with R = H, methyl, phenyl, perfluorophenyl, chloride, and cyanide). Two of the new metal complexes have also been characterized by X-ray analysis. In all the R-pm-tpy ligands, the pyrimidinyl and terpyridyl groups are coplanar, allowing an extended delocalization of acceptor orbital of the metal-to-ligand charge-transfer (MLCT) excited state. The absorption spectra, redox behavior, and luminescence properties of the new Ru(II) complexes have been investigated. In particular, the photophysical properties of these species are significantly better compared to those of [Ru(tpy)2]2+ and well comparable with those of the best emitters of Ru(II) polypyridine family containing tridentate ligands. Reasons for the improved photophysical properties lie at the same time in an enhanced MLCT-MC (MC = metal centered) energy gap and in a reduced difference between the minima of the excited and ground states potential energy surfaces. The enhanced MLCT-MC energy gap leads to diminished efficiency of the thermally activated pathway for the radiationless process, whereas the similarity in ground and excited-state geometries causes reduced Franck Condon factors for the direct radiationless decay from the MLCT state to the ground state of the new complexes in comparison with [Ru(tpy)2]2+ and similar species.     

Synthesis and properties of the elusive ruthenium(II) complexes of 4'-cyano-2,2':6',2' '-terpyridine

The heteroleptic and homoleptic ruthenium(II) complexes of 4'-cyano-2,2':6',2' '-terpyridine are synthesized by palladium catalyzed cyanation of the corresponding Ru(II) complexes of 4'-chloro-2,2':6',2' '-terpyridine. The introduction of the strongly electron-withdrawing cyano group into the Ru(tpy)(2)(2+) moiety dramatically changes its photophysical and redox properties as well as prolongs its room temperature excited-state lifetime.     

Synthesis, characterization and electrochemistry of 4'-functionalized 2,2':6',2'-terpyridine ruthenium(II) complexes and their biological activity

The synthesis and characterization of Ru(II) terpyridine complexes derived from 4'-functionalized 2,2':6',2'-terpyridine ligands by a multi step procedure have been described. The complexes are redox-active, showing both metal-centred (oxidation) and ligand-centred (reduction) processes. The antibacterial and antifungal activity of the synthesized ruthenium(II) complexes [Ru(attpy)2](PF6)2 (attpy = 4'-(4-acryloyloxymethylphenyl)-2,2':6',2'-terpyridine); [Ru(mttpy)2](PF6)2 (mttpy = 4'-(4-methacryloyloxymethylphenyl)-2,2':6',2'- terpyridine); [Ru(mttpy)(MeOPhttpy)](PF6)2 (MeOPhttpy = 4'-(4-methoxyphenyl)-2,2':6',2'-terpyridine); and [Ru(mttpy)(ttpy)](PF6)2 (ttpy = 4'-(4-methylphenyl)-2,2':6',2'-terpyridine) were tested against four human pathogens (Proteus vulgaris, Proteus mirabilis, Pseudomonas aeruginosa and Escherichia coli) and five plant pathogens (Curvularia lunata, Fusarium oxysporum, Fusarium udum, Macrophomina phaseolina and Rhizoctonia solani) by the well diffusion method and MIC values of the complexes are reported. A biological study of the complexes indicated that the complexes [Ru(mttpy)2](PF6)2 and [Ru(mttpy)(MeOPhttpy)](PF6)2 exhibit very good activity against most of the test pathogens and their activity is better than those of some of the commercially available antibiotics like tetracycline and the fungicide carbendazim.     

Using End Groups to Tune the Linear and Nonlinear Optical Properties of Bis(dioxaborine)‐Terminated Polymethine Dyes

Six anionic pentamethine dyes with different 2,2‐difluoro‐4‐aryl‐1,3,2(2 H)‐dioxaborin‐6‐yl termini were synthesized and isolated as tetra‐n‐octylammonium salts with a variety of aryl groups appended to increase conjugation beyond the dioxaborine termini. The increased conjugation was expected to decrease the energy of the lowest‐lying excited state, and increase the transition dipole moment linking this state to the ground state, which would be anticipated to result in an increase in the real part of the third‐order polarizability, Re(γ). UV/Vis‐NIR absorption spectroscopy indicates that the absorption maxima in DMSO vary from 691 to 761 nm, with the longest wavelength transitions observed for a derivative where the aryl group is 4‐nitrophenyl. Closed‐aperture Z‐scan measurements at 1.3 μm in DMSO indicate that Re(γ) varies from ?2.9×10^?33 to ?5.4×10^?33 esu in these systems. The largest magnitude of Re(γ) was observed for a dye with E‐4‐styrylphenyl aryl groups. This result can be rationalized using a two‐state expression which relates Re(γ) to the energy and transition dipole moment of the transition from the ground state to the lowest‐lying excited state. A nonamethine analogue of this compound was also synthesized and exhibits a slightly larger Re(γ) with respect to a previously reported bis(dioxaborine)‐terminated nonamethine. The extension of conjugation beyond the dioxaborine termini seems to result in an overall increase in Re(γ). However, the effects are smaller than those found by increasing conjugation in the polymethine bridge due to reduced participation of terminal groups in the HOMO.     

Preparation and crystal structure of binuclear chloro{6-[[chloro(triphenylphosphine)platinum](mesitylimino)methyl]pyridin-2-yl}bis(triphenylphosphine)platinum(II)

Treatment of N,N′-bis(mesityl)pyridine-2,6-carboxyimidoyl dichloride, 1, in toluene solution with [Pt(PPh₃)₄] at 100 °C afforded a novel platinacyclic compound, 3, in 63% yield, instead of the expected compound 2. The molecular and crystal structures of the title compound, 3, have been determined by the single crystal X-ray diffraction technique. The coordination geometries around the Pt atoms are distorted square-planar. In the crystal structure, the molecules are linked by a pair of C–H···N hydrogen bonds into a centrosymmetric dimer with an ring, centred at (1/2,1/2,1/2).     

The first example of a Pt...Pt interaction in platinum(ii) complexes bearing bulky tri-tert-butyl-2,2':6',2'-terpyridine pendants via conformational control of the calix[4]arene moiety

An unprecedented short Pt...Pt contact between sterically bulky Pt((t)Bu(3)trpy) alkynyl moieties has been observed in the X-ray crystal structure of a dinuclear platinum(ii) complex bridged by a diethynylcalix[4]arene derivative; the complex in its crystalline state showed a red shift in the emission maxima at 298 K and 77 K relative to its powder form, which has been attributed to the presence of a metal-metal interaction in the crystal lattice.     

Syntheses and Characterizations of Luminescent Complexes [(BINAP)Pt(C≡CC6H4R-p)2] (R = H, 1; CH3, 2) (BINAP = 2,2''-Bis(diphenylphosphino)-1,1''-binaphthyl)

[(BINAP)Pt(C≡CC6H4R-p)2] (R = H, 1; CH3, 2) (BINAP = 2,2'-bis(diphenylphos- phino)-1,1'-binaphthyl) were synthesized and characterized by X-ray crystallography. Complex 1 crystallizes in triclinic, space group P with a = 11.699(3), b = 12.512(3), c = 15.611(4)(A), α = 93.277(3),β= 97.626(2), γ = 97.375(14)o, V = 2239.9(9)(A)3, Mr = 1014.92, Z = 2, Dc = 1.505 g/cm3, F(000) = 1010, μ(MoKα) = 3.244 mm-1, the final R = 0.0338 and wR = 0.0905 for 7738 observed reflections (I > 2σ(I)). Complex 2 crystallizes in monoclinic, space group P21/n with a = 18.03690 (10), b = 13.06060(10), c = 21.6913(3)(A), β= 96.5430(10)o, V = 5076.60(9)(A)3, Mr = 1132.94, Z = 4, Dc = 1.482 g/cm3, F(000) = 2272, μ(MoKα) = 2.973 mm-1, the final R = 0.0481 and wR = 0.0893 for 8916 observed reflections (I > 2σ(I)). Both complexes emit intensively photoluminescence in both solid state and fluid solution due to MLCT (Pt→-C≡CC6H4R-p) emissive state.     

4'-(5'-R-pyrimidyl)-2,2':6',2'-terpyridyl (R = H, OEt, Ph, Cl, CN) platinum(II) phenylacetylide complexes: synthesis and photophysics

A series of new square-planar 4'-(5'-R-pyrimidyl)-2,2':6',2'-terpyridyl platinum(II) phenylacetylide complexes ( 1a- 5a) bearing different substituents (R = H, OEt, Ph, Cl, CN) on the pyrimidyl ring have been synthesized and characterized. The electronic absorption, photoluminescence, and triplet transient difference absorption spectra were investigated. All of the complexes exhibit broad, moderately strong absorption between 400 and 500 nm that can be tentatively assigned to the metal-to-ligand charge transfer ( (1)MLCT) transition, possibly mixed with some ligand-to-ligand charge transfer ( (1)LLCT) character. Photoluminescence arising from the (3)MLCT state was observed both in fluid solutions at room temperature and in a rigid matrix at 77 K. The (1)MLCT/ (1)LLCT absorption bands and the (3)MLCT emission bands for 1a- 5a red-shift in comparison to those of the corresponding 4'-toly-2,2':6',2'-terpyridyl platinum(II) phenylacetylide complex. In addition, the energies of the (1)MLCT/ (1)LLCT absorption and the (3)MLCT emission bands exhibit a linear correlation with the Hammett constant (sigma p) of the 5'-substituent on the pyrimidyl ring. The lifetime of the (3)MLCT emission at room temperature is governed by the energy gap law. The triplet transient difference absorption spectra of 1a- 5a exhibit a broad absorption band from 500 to 800 nm, and a bleaching band between 420 and 500 nm. Complex 5a, which contains the -CN substituent, exhibits a lower-energy triplet absorption band at 785 nm and a shorter lifetime (130 ns) in CH 3CN than 2a, which has the -OEt substituent, does (lambda T1-Tn (max) = 720 nm, tau T = 660 ns). The triplet excited-state absorption coefficients at the band maxima for 1a- 5a vary from 36 600 L.mol (-1).cm (-1) to 115 090 L.mol (-1).cm (-1), and the quantum yields of the triplet excited-state formation range from 0.19 to 0.66. All complexes exhibit a moderate nonlinear transmission for nanosecond laser pulses at 532 nm. Moreover, these complexes can generate singlet oxygen efficiently in air-saturated CH 3CN solutions, with the singlet oxygen generation quantum yield (Phi Delta) varying from 0.24 to 0.46.     

Synthesis,one‐ and two‐photon properties of poly[9,10‐bis(3,4‐bis(2‐ethylhexyl‐oxy)phenyl)‐2,6‐anthracenevinylene‐alt‐N‐octyl‐3,6‐/2,7‐carbazolevinylene]

The synthesis, one‐ and two‐photon absorption (TPA) and emission properties of two novel 2,6‐anthracenevinylene‐based copolymers, poly[9,10‐bis(3,4‐bis(2‐ethylhexyloxy)phenyl)‐2,6‐anthracenevinylene‐alt‐N‐octyl‐3,6‐carbazolevinyl‐ene] ( P1 ) and poly[9,10‐bis(3,4‐bis(2‐ethylhexyloxy)phenyl)‐2,6‐anthracenevinyl‐ene‐alt‐N‐octyl‐2,7‐carbazolevinylene] ( P2 ) were reported. The as‐synthesized polymers have the number‐average molecular weights of 1.56 × 10⁴ for P1 and 1.85 × 10⁴ g mol^?1 for P2 and are readily soluble in common organic solvents. They emit strong bluish‐green one‐ and two‐photon excitation fluorescence in dilute toluene solution (? _P1 = 0.85, ? _P2 = 0.78, λ_em( P1 ) = 491 nm, λ_em( P2 ) = 483 nm). The maximal TPA cross‐sections of P1 and P2 measured by the two‐photon‐induced fluorescence method using femtosecond laser pulses in toluene are 840 and 490 GM per repeating unit, respectively, which are obviously larger than that (210 GM) of poly[9,10‐bis‐(3,4‐bis(2‐ethylhexyloxy) phenyl)‐2,6‐anthracenevinylene], indicating that the poly(2,6‐anthracenevinylene) derivatives with large TPA cross‐sections can be obtained by inserting electron‐donating moieties into the polymer backbone. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 463–470, 2010     

Electrochemical polymerization of (2-dodecyl-4, 7-di (thiophen-2-yl)-2H-benzo[d][1,2,3] triazole): a novel matrix for biomolecule immobilization

A recently synthesized conducting polymer [poly(2-dodecyl-4,7-di(thiophen-2-yl)-2H-benzo[d][1,2,3]triazole (PTBT)] was tested as a platform for biomolecule immobilization. After electrochemical polymerization of the monomer (TBT) on graphite electrodes, immobilization of glucose oxidase (GOx,β-D-glucose: oxygen-1-oxidoreductase, EC 1.1.3.4) was carried out. To improve the interactions between the enzyme and hydrophobic alkyl chain on the polymeric structure, GOx and isoleucine (Ile) amino acid were mixed in sodium phosphate buffer (pH 7.0) with a high ionic strength (250 × 10(-3) M). The solution is then casted on the polymer film, and the amino groups in the protein structure were crosslinked using glutaraldehyde (GA) as the bifunctional agent. Finally, the surface was covered with a perm-selective membrane. Consequently, cross-linked enzyme crystal (CLEC) like assembles with regular shapes were observed after immobilization. Microscopic techniques such as scanning electron microscopy (SEM) and fluorescence microscopy were used to monitor the surface morphologies of both the polymer and the bioactive layer. Electrochemical responses of the enzyme electrodes were measured by monitoring O(2) consumption in the presence of glucose at -0.7 V. The optimized biosensor showed a very good linearity between 0.05 and 2.5 × 10(-3) M with a 52 s response time and a detection limit (LOD) of 0.029 × 10(-3) M to glucose. Also, kinetic parameters, operational and storage stabilities were determined. K(m) and I(max) values were found as 4.6 × 10(-3) M and 2.49 μA, respectively. It was also shown that no activity was lost during operational and storage conditions. Finally, proposed system was applied for glucose biomonitoring during fermentation in yeast culture where HPLC was used as the reference method to verify the data obtained by the proposed biosensor.     

Synthesis, luminescence, and electrochemical studies of tris(homoleptic) ruthenium(II) and osmium(II) complexes of 6'-tolyl-2,2':4',2'-terpyridine

The synthesis and photophysical and electrochemical properties of tris(homoleptic) complexes [Ru(tpbpy)3](PF6)2 (1) and [Os(tpbpy)3](PF6)2 (2) (tpbpy = 6'-tolyl-2,2':4',2' '-terpyridine) are reported. The ligand tpbpy is formed as the side product during the synthesis of 4'-tolyl-2,2':6',2' '-terpyridine (ttpy) and characterized by single-crystal X-ray diffraction: monoclinic, P21/c. The tridentate tpbpy coordinates as a bidentate ligand. The complexes 1 and 2 exhibit two intense absorption bands in the UV region (200-350 nm) assignable to the ligand-centered (1LC) pi-pi* transitions. The ruthenium(II) complex exhibits a broad absorption band at 470 nm while the osmium(II) complex exhibits an intense absorption band at 485 nm and a weak band at 659 nm assignable to the MLCT (dpi-pi*) transitions. A red shifting of the dpi-pi* MLCT transition is observed on going from the Ru(II) to the Os(II) complex as expected from the high-lying dpi Os orbitals. These complexes exhibit ligand-sensitized emission at 732 and 736 nm, respectively, upon light excitation onto their MLCT band through excitation of higher energy LC bands at room temperature. The MLCT transitions and the emission maxima of 1 and 2 are substantially red-shifted compared to that of [Ru(bpy)3](PF6)2 and [Os(bpy)3](PF6)2. The emission of both the complexes in the presence of acid is completely quenched indicating that the emission is not due to the protonation of the coordinated ligands. Our results indicate the occurrence of intramolecular energy transfer from the ligand to the metal center. Both the complexes undergo quasi-reversible metal-centered oxidation, and the E1/2 values for the M(II)/M(III) redox couples (0.94 and 0.50 V versus Ag/Ag+ for 1 and 2, respectively) are cathodically shifted with respect to that of [Ru(bpy)3](PF6)2 and [Os(bpy)3](PF6)2 (E1/2 = 1.28 and 1.09 V versus Ag/Ag+, respectively). The tris(homoleptic) Ru(II) and Os(II) complexes 1 and 2 could be used to construct polynuclear complexes by using the modular synthetic approach in coordination compounds by exploiting the coordinating ability of the pyridine substituent. Furthermore, these complexes offer the possibility of studying the influence of electron-withdrawing and electron-donating substituents on the photophysical properties of Ru(II) and Os(II) polypyridine complexes.     

Hyperbranched polyester poly[3-(morpholin-4-yl)propionates] and their copper(II) complexes

Novel polydentate ligands on the basis of second- and third-generation hyperbranched polyesters containing terminal poly[3-(morpholin-4-yl)propionate] groups and their 6 : 1 and 13 : 1 polynuclear copper(II) complexes were synthesized. The degree of functionalization of the polyesters with morpholine increases in going from the second (56%) to third generation (68%). According to IR and electronic spectroscopy data, each coordination entity in the complexes is an isolated paramagnetic center of the formula CuN₂O₂Solv₂ (Solv = H₂O, DMSO).     

Synthesis and Structure of Trimethylplatinum(IV) Iodide Complex of 4'-(4-Methoxyphenyl)-2,2':6',2'-terpyridine Ligand and its Halogen Bonding Property

The synthesis and structural characterization of a new trimethylplatinum(IV) iodide complex of 4'-(4-methoxyphenyl)-2,2':6',2''-terpyridine ligand L, {PtMe₃IL} ( 1 ) is reported. The X-ray crystal structure shows that the terpyridine ligand L binds the platinum(IV) metal center in bidentate fashion, which is well supported by the ¹H NMR spectrum of 1 . The complex 1 upon crystallization with 1,4-diiodotetrafluorobenzene (DITFB) forms the halogen bonded complex 1a ( 1· DITFB). The structural investigation shows that 1a exhibits the halogen bonding interaction in which the non-coordinated pyridyl nitrogen acts as halogen bond acceptors by forming I ··· N interaction with iodine atom of DITFB. In addition iodine atom of complex 1 also acts as weak halogen bond acceptor.