Enhancing the Acceptor Character of Conjugated Organoborane Macrocycles: A Highly Electron‐Deficient Hexaboracyclophane

We introduce a new boron‐doped cyclophane, the hexabora[1₆]cyclophane B6‐^FMes , in which six tricoordinate borane moieties alternate with short conjugated p‐phenylene linkers. Exocyclic 2,4,6‐tris(trifluoromethyl)phenyl (^FMes) groups serve not only to further withdraw electron density but at the same time sterically shield the boron atoms, resulting in a macrocycle that is both highly electron‐deficient and stable. The optical and electronic properties are compared with those of related linear oligomers and the electronic structure is further evaluated by computational methods. The studies uncover unique properties of B6‐^FMes , including a low‐lying and extensively delocalized LUMO and a wide HOMO–LUMO gap, which arise from the combination of a cyclic π‐system, strong electronic communication between the closely spaced borons, and the attachment of electron‐deficient pendent groups. The binding of small anions to the electron‐deficient macrocycle and molecular model compounds is investigated and emissive exciplexes are detected in aromatic solvents.     

Highly Stable,Readily Reducible,Fluorescent, Trifluoromethylated 9-Borafluorenes

Three different perfluoroalkylated borafluorenes ( ^F Bf ) were prepared and their electronic and photophysical properties were investigated. The systems have four trifluoromethyl moieties on the borafluorene moiety as well as two trifluoromethyl groups at the ortho positions of their exo-aryl moieties. They differ with regard to the para substituents on their exo-aryl moieties, being a proton ( ^F Xyl^FBf , ^FXyl: 2,6-bis(trifluoromethyl)phenyl), a trifluoromethyl group ( ^F Mes^FBf , ^FMes: 2,4,6-tris(trifluoromethyl)phenyl) or a dimethylamino group ( p -NMe₂-^FXyl^FBf , p-NMe₂-^FXyl: 4-(dimethylamino)-2,6-bis(trifluoromethyl)phenyl), respectively. All derivatives exhibit extraordinarily low reduction potentials, comparable to those of perylenediimides. The most electron-deficient derivative ^F Mes^FBf was also chemically reduced and its radical anion isolated and characterized. Furthermore, all compounds exhibit very long fluorescent lifetimes of about 250 ns up to 1.6 μs; however, the underlying mechanisms responsible for this differ. The donor-substituted derivative p -NMe₂-^FXyl^FBf exhibits thermally activated delayed fluorescence (TADF) from a charge-transfer (CT) state, whereas the ^F Mes^FBf and ^F Xyl^FBf borafluorenes exhibit only weakly allowed locally excited (LE) transitions due to their symmetry and low transition-dipole moments.     

Highly Electron‐Deficient and Air‐Stable Conjugated Thienylboranes

Introduced herein is a series of conjugated thienylboranes, which are inert to air and moisture, and even resist acids and strong bases. X‐ray analyses reveal a coplanar arrangement of the thiophene rings, an arrangement which facilitates p–π conjugation through the boron atoms despite the presence of highly bulky 2,4,6‐tri‐tert‐butylphenyl (Mes*) or 2,4,6‐tris(trifluoromethyl)phenyl (^FMes) groups. Short B???F contacts, which lead to a pseudotrigonal bipyramidal geometry in the ^FMes species, have been further studied by DFT and AIM analysis. In contrast to the Mes* groups, the highly electron‐withdrawing ^FMes groups do not diminish the Lewis acidity of boron toward F^? anions. These compounds can be lithiated or iodinated under electrophilic conditions without decomposition, thus offering a promising route to larger conjugated structures with electron‐acceptor character.     

Photochemical Bromination of 2,5-Dimethylbenzoic Acid as Key Step of an Improved Alkyne-Functionalized Blue Box Synthesis**

Cyclobis(paraquat-p-phenylene), also known as “blue box”, is a highly electron-deficient macrocycle, widely used as a molecular receptor for small electron-rich molecules. Inserting a reactive functional group onto the molecular structure of this cyclophane is paramount for its inclusion into complex architectures. To this aim, including an alkyne moiety would be ideal, because it can participate in click reactions. However, the synthesis of such alkyne-functionalized cyclophane suffers from several drawbacks: the use of toxic and expensive CCl₄, the need for high-pressure reactors, and overall low yield. We have revised the existing synthesis of this cyclophane derivative bearing an alkyne moiety, to overcome all these limitations. In particular, photochemical radical bromination is adopted to obtain a sensitive intermediate. We demonstrated that the synthesized host molecule can be functionalized via click reactions and take part in radical-radical interactions. Our work makes a key functionalized paraquat macrocycle more accessible, facilitating the development of novel redox-responsive systems.     

Geometry and electronic properties of alkali metal (rubidium) doped boron clusters

Alkali metal-doped boron clusters have captured much attention because of their novel electronic properties and structural evolution. In the study of RbB_n^0/− (n = 2–12) clusters, the minimum global search of the potential energy surface and structure optimization at the level of PBE1PBE by using the CALYPSO method and Gaussian package coupled with DFT calculation; the geometrical structures and electronic properties are systematically investigated. At n = 8, the ground-state structures are composed of an Rb atom above B atoms, forming a structurally stable pagoda cone. By stability analysis and charge transfer calculation, the RbB₈⁻ cluster shows more stability. It found that s-p hybridization between Rb atom and B atoms as well as s-p hybridization between B atoms is one of the reasons for the outstanding stability exhibited in the RbB₈^0/− clusters by using DOS and HOMO–LUMO orbital contour maps. The chemical bonding of the RbB₈^0/− groups was analyzed by using the AdNDP method, and B atoms with larger numbers readily form multi-center chemical bonds with the Rb atom. From the results of the bonding analysis, the interaction between the Rb atom and B atoms strengthens the stability of the RbB₈^0/− clusters. It is hoped that this work provides a direction for experimental manipulation.     

Homolytic C−H Bond Activation by Phosphine−Quinone-Based Radical Ion Pairs

Herein, we present the formation of transient radical ion pairs (RIPs) by single-electron transfer (SET) in phosphine−quinone systems and explore their potential for the activation of C−H bonds. PMes₃ (Mes=2,4,6-Me₃C₆H₂) reacts with DDQ (2,3-dichloro-5,6-dicyano-1,4-benzoquinone) with formation of the P−O bonded zwitterionic adduct Mes₃P−DDQ ( 1 ), while the reaction with the sterically more crowded PTip₃ (Tip=2,4,6-iPr₃C₆H₂) afforded C−H bond activation product Tip₂P(H)(2-[CMe₂(DDQ)]-4,6-iPr₂-C₆H₂) ( 2 ). UV/Vis and EPR spectroscopic studies showed that the latter reaction proceeds via initial SET, forming RIP [PTip₃]⋅⁺[DDQ]⋅⁻, and subsequent homolytic C−H bond activation, which was supported by DFT calculations. The isolation of analogous products, Tip₂P(H)(2-[CMe₂{TCQ−B(C₆F₅)₃}]-4,6-iPr₂-C₆H₂) ( 4 , TCQ=tetrachloro-1,4-benzoquinone) and Tip₂P(H)(2-[CMe₂{oQ^tBu−B(C₆F₅)₃}]-4,6-iPr₂-C₆H₂) ( 8 , oQ^tBu=3,5-di-tert-butyl-1,2-benzoquinone), from reactions of PTip₃ with Lewis-acid activated quinones, TCQ−B(C₆F₅)₃ and oQ^tBu−B(C₆F₅)₃, respectively, further supports the proposed radical mechanism. As such, this study presents key mechanistic insights into the homolytic C−H bond activation by the synergistic action of radical ion pairs.     

Reactions of Diethylazo-Dicarboxylate with Frustrated Lewis Pairs

Reactions of PAr₃/B(C₆F₅)₃ (Ar=o-Tol, Mes, Ph) FLPs with diethyl azodicarboxylate (DEAD) afford the corresponding FLP addition products 1 – 3 in which P−N and B−O linkages are formed. In contrast, the reaction of BPh₃, PPh₃ and DEAD gave product 4 where P−N and N−B linkages were confirmed. In all cases, other binding modes were computed to be both higher in energy and readily distinguishable by ³¹P and ¹¹B NMR parameters. These data illustrate the influence of steric demands and electronic structures on the nature of the products of FLP reactions with DEAD.     

A Macrocycle Based on a Heptagon-Containing Hexa-peri-hexabenzocoronene

A cyclophane is reported incorporating two units of a heptagon-containing extended polycyclic aromatic hydrocarbon (PAH) analogue of the hexa-peri-hexabenzocoronene (HBC) moiety (hept-HBC). This cyclophane represents a new class of macrocyclic structures that incorporate for the first time seven-membered rings within extended PAH frameworks. The saddle curvature of the hept-HBC macrocycle units induced by the presence of the nonhexagonal ring along with the flexible alkyl linkers generate a cavity with shape complementarity and appropriate size to enable π interactions with fullerenes. Therefore, the cyclophane forms host–guest complexes with C₆₀ and C₇₀ with estimated binding constants of K_a=420±2 m ⁻¹ and K_a=(6.49±0.23)×10³ m ⁻¹, respectively. As a result, the macrocycle can selectively bind C₇₀ in the presence of an excess of a mixture of C₆₀ and C₇₀.     

A Systematic Study of Structure and E−H Bond Activation Chemistry by Sterically Encumbered Germylene Complexes

A series of new germylene compounds has been synthesized offering systematic variation in the σ‐ and π‐capabilities of the α‐substituent and differing levels of reactivity towards E?H bond activation (E=H, B, C, N, Si, Ge). Chloride metathesis utilizing [(terphenyl)GeCl] proves to be an effective synthetic route to complexes of the type [(terphenyl)Ge(ER_n)] ( 1 – 6 : ER_n=NHDipp, CH(SiMe₃)₂, P(SiMe₃)₂, Si(SiMe₃)₃ or B(NDippCH)₂; terphenyl=C₆H₃Mes₂‐2,6=Ar^Mes or C₆H₃Dipp₂‐2,6=Ar^Dipp; Dipp=C₆H₃iPr₂‐2,6, Mes=C₆H₂Me₃‐2,4,6), while the related complex [{(Me₃Si)₂N}Ge{B(NDippCH)₂}] ( 8 ) can be accessed by an amide/boryl exchange route. Metrical parameters have been probed by X‐ray crystallography, and are consistent with widening angles at the metal centre as more bulky and/or more electropositive substituents are employed. Thus, the widest germylene units (θ>110°) are found to be associated with strongly σ‐donating boryl or silyl ancillary donors. HOMO–LUMO gaps for the new germylene complexes have been appraised by DFT calculations. The aryl(boryl)‐germylene system [Ar^MesGe{B(NDippCH)₂}] ( 6 ‐Mes), which features a wide C‐Ge‐B angle (110.4(1)°) and (albeit relatively weak) ancillary π‐acceptor capabilities, has the smallest HOMO–LUMO gap (119 kJ mol^?1). These features result in 6 ‐Mes being remarkably reactive, undergoing facile intramolecular C?H activation involving one of the mesityl ortho‐methyl groups. The related aryl(silyl)‐germylene system, [Ar^MesGe{Si(SiMe₃)₃}] ( 5 ‐Mes) has a marginally wider HOMO–LUMO gap (134 kJ mol^?1), rendering it less labile towards decomposition, yet reactive enough to oxidatively cleave H₂ and NH₃ to give the corresponding dihydride and (amido)hydride. Mixed aryl/alkyl, aryl/amido and aryl/phosphido complexes are unreactive, but amido/boryl complex 8 is competent for the activation of E?H bonds (E=H, B, Si) to give hydrido, boryl and silyl products. The results of these reactivity studies imply that the use of the very strongly σ‐donating boryl or silyl substituents is an effective strategy for rendering metallylene complexes competent for E?H bond activation.     

Stereochemical Behavior of Pairs of P-stereogenic Phosphanyl Groups at the Dimethylxanthene Backbone

The P-stereogenic bis(phosphanes) 7 and 9 , featuring pairs of P(Mes)-ethynyl or vinyl substituents at the dimethyl xanthene backbone show rather low barriers of stereochemical inversion at phosphorus. π-Conjugative effects are probably causing these low inversion barriers. Compound 7 reacted with B(C₆F₅)₃ to form the nine-membered heterocyclic product 10 , featuring a [P]−C≡C−B(C₆F₅)₃ substituent. Compound 7 was converted to the bis[P(Mes)vinyl] xanthene derivative 9 , which gave the zwitterionic P(H)(Mes)−CH=CH−B(C₆F₅)₃ containing product 16 upon treatment with B(C₆F₅)₃. Thermally induced epimerization barriers at phosphorus of ca. 20 to 27 kcal mol⁻¹ were calculated by DFT for the alkenyl- and alkynyl-P derived systems 6 to 9 , 15 and 16 and experimentally determined for the examples 7 and 16 .     

Aluminium Diphosphamethanides: Hidden Frustrated Lewis Pairs

The synthesis and characterisation of two aluminium diphosphamethanide complexes, [Al(tBu)₂{κ²P,P′‐Mes*PCHPMes*}] ( 3 ) and [Al(C₆F₅)₂{κ²P,P′‐Mes*PCHPMes*}] ( 4 ), and the silylated analogue, Mes*PCHP(SiMe₃)Mes* ( 5 ), are reported. The aluminium complexes feature four‐membered PCPAl core structures consisting of diphosphaallyl ligands. The silylated phosphine 5 was found to be a valuable precursor for the synthesis of 4 as it cleanly reacts with the diaryl aluminium chloride [(C₆F₅)₂AlCl]₂. The aluminium complex 3 reacts with molecular dihydrogen at room temperature under formation of the acyclic σ²λ³,σ³λ³‐diphosphine Mes*PCHP(H)Mes* and the corresponding dialkyl aluminium hydride [tBu₂AlH]₃. Thus, 3 belongs to the family of so‐called hidden frustrated Lewis pairs.     

The Non-Ancillary Nature of Trimethylsilylamide Substituents in Boranes and Borinium Cations

The known boranes (R(Me₃Si)N)₂BF (R=Me₃Si 1 , tBu 2 , C₆F₅ 3 , o-tol 4 , Mes 5 , Dipp 6 ) and borinium salts (R(Me₃Si)N)₂B][B(C₆F₅)₄] (R=Me₃Si 7 , tBu 8 ) are prepared and fully characterized. Compound 7 is shown to react with phosphines to generate [R₃PSiMe₃]⁺ and [R₃PH]⁺ (R=Me, tBu). Efforts to generate related borinium cations via fluoride abstraction from (R(Me₃Si)N)₂BF (R=C₆F₅ 3 , o-tol 4 , Mes 5 ) gave complex mixtures suggesting multiple reaction pathways. However for R=Dipp 6 , the species [(μ-F)(SiMe₂N(Dipp))₂BMe][B(C₆F₅)₄] was isolated as the major product, indicating methyl abstraction from silicon and F/Me exchange on boron. These observations together with state-of-the-art DFT mechanistic studies reveal that the trimethylsilyl-substituents do not behave as ancillary subsitutents but rather act as sources of proton, SiMe₃ and methyl groups.     

A Macrocycle Based on a Heptagon‐Containing Hexa‐peri‐hexabenzocoronene

A cyclophane is reported incorporating two units of a heptagon‐containing extended polycyclic aromatic hydrocarbon (PAH) analogue of the hexa‐peri‐hexabenzocoronene (HBC) moiety (hept‐HBC). This cyclophane represents a new class of macrocyclic structures that incorporate for the first time seven‐membered rings within extended PAH frameworks. The saddle curvature of the hept‐HBC macrocycle units induced by the presence of the nonhexagonal ring along with the flexible alkyl linkers generate a cavity with shape complementarity and appropriate size to enable π interactions with fullerenes. Therefore, the cyclophane forms host–guest complexes with C₆₀ and C₇₀ with estimated binding constants of K_a=420±2 m ^?1 and K_a=(6.49±0.23)×10³ m ^?1, respectively. As a result, the macrocycle can selectively bind C₇₀ in the presence of an excess of a mixture of C₆₀ and C₇₀.     

Exploring the Reactivity of B-Connected Carboranylphosphines in Frustrated Lewis Pair Chemistry: A New Frame for a Classic System

The primary phosphines MesPH₂ and tBuPH₂ react with 9-iodo-m-carborane yielding B9-connected secondary carboranylphosphines 1,7-H₂C₂B₁₀H₉-9-PHR (R=2,4,6-Me₃C₆H₂ (Mes; 1 a ), tBu ( 1 b )). Addition of tris(pentafluorophenyl)borane (BCF) to 1 a , b resulted in the zwitterionic compounds 1,7-H₂C₂B₁₀H₉-9-PHR(p-C₆F₄)BF(C₆F₅)₂ ( 2 a , b ) through nucleophilic para substitution of a C₆F₅ ring followed by fluoride transfer to boron. Further reaction with Me₂SiHCl prompted a H−F exchange yielding the zwitterionic compounds 1,7-H₂C₂B₁₀H₉-9-PHR(p-C₆F₄)BH(C₆F₅)₂ ( 3 a , b ). The reaction of 2 a , b with one equivalent of R'MgBr (R’=Me, Ph) gave the extremely water-sensitive frustrated Lewis pairs 1,7-H₂C₂B₁₀H₉-9-PR(p-C₆F₄)B(C₆F₅)₂ ( 4 a , b ). Hydrolysis of the B−C₆F₄ bond in 4 a , b gave the first tertiary B-carboranyl phosphines with three distinct substituents, 1,7-H₂C₂B₁₀H₉-9-PR(p-C₆F₄H) ( 5 a , b ). Deprotonation of the zwitterionic compounds 2 a , b and 3 a , b formed anionic phosphines [1,7-H₂C₂B₁₀H₉-9-PR(p-C₆F₄)BX(C₆F₅)₂]⁻[DMSOH]⁺ (R=Mes, X=F ( 6 a ), R=tBu, X=F ( 6 b ); R=Mes, X=H ( 7 a ), R=tBu, X=H ( 7 b )). Reaction of 2 a , b with an excess of Grignard reagents resulted in the addition of R’ at the boron atom yielding the anions [1,7-H₂C₂B₁₀H₉-9-PR(p-C₆F₄)BR’(C₆F₅)₂]⁻ (R=Mes, R’=Me ( 8 a ), R=tBu, R’=Me ( 8 b ); R=Mes, R’=Ph ( 9 a ), R=tBu, R’=Ph ( 9 b )) with [MgBr(Et₂O)_n]⁺ as counterion. The ability of the zwitterionic compounds 3 a , b to hydrogenate imines as well as the Brønsted acidity of 3 a were investigated.     

Low-Coordinate Monomeric Zinc Hydride Complexes with Encapsulating Dipyrromethene Ligands and Reactivity with B(C6F5)3

The dipyrromethene (DPM) ligand is the key to isolation of monomeric Zn hydride complexes with tricoordinate zinc centers. A range of ^RDPM ligands with various substituents in the pole position (1,9-positions) were prepared: R = tBu, adamantyl (Ad), mesityl (Mes), 2,6-diisopropylphenyl (DIPP), 2,4,6-triphenylphenyl (Mes*), or 9-anthracenyl (Anth). Reaction of the ligands with Et₂Zn gave a series of (^RDPM)ZnEt complexes, which were converted with I₂ to the corresponding (^RDPM)ZnI compounds. The latter reacted by salt metathesis with KN(iPr)HBH₃ to the series of Zn hydride complexes (^RDPM)ZnH. For ligands with the larger Mes* and Anth substituents, (^RDPM)ZnEt was converted to (^RDPM)ZnOSiPh₃, which after reaction with PhSiH₃ gave the hydrides. While Zn hydride complexes with R = tBu or Ad are dimeric, all complexes with aryl-substituents are monomeric. The aryl groups span a cavity around the metal, blocking dimerization and causing a high-field shift of the ¹H NMR signals due to the ASIS effect. Attempted abstraction of the hydride with B(C₆F₅)₃ led to cleavage of the B-C₆F₅ bond.     

Thermal and Photophysical Properties of Highly Quadrupolar Liquid-Crystalline Derivatives of the [closo-B12H12]2− Anion

Two series of 1,12-bis-zwitterionic derivatives of the [closo-B₁₂H₁₂]²⁻ anion ( B ), containing either two 4-alkoxypyridinium groups ( 1B[n]-p ) or one 4-alkoxypyridinium and one 4-pentylthianium groups ( 2B[n]-p ), were prepared and their structural (XRD, DFT), thermal, and photophysical properties were compared with those of the analogous derivatives of the [closo-B₁₀H₁₀]²⁻ anion ( 1A[n]-p and 2A[n]-p ). Some 1,7-derivatives of B were isolated and investigated. Both series 1[n] and 2[n] exhibit nematic and crystalline polymorphism; the 12-vertex derivatives ( B ) have higher transition temperatures than those of the 10-vertex analogues ( A ). All compounds fluoresce with quantum yields higher for 1B (Φ_F=0.37 for 1B[7]-p and Φ_F=0.27 for 2B[7]-p ) than those for the 10-vertex analogues (Φ_F=0.04 for 2A[5]-p ). DFT calculations demonstrate an order of magnitude lower first hyperpolarizability, β_(−ω,ω,0), for 2B[7]-p than that for the 10-vertex analogue 2A[7]-p (1.7×10⁻³⁰ vs. 18.9×10⁻³⁰ esu at ω=0).     

Phosphorus Centers of Different Hybridization in Phosphaalkene‐Substituted Phospholes

Phosphole‐substituted phosphaalkenes (PPAs) of the general formula Mes*P?C(CH₃)?(C₄H₂P(Ph))?R 5 a – c (Mes*=2,4,6‐tBu₃Ph; R=2‐pyridyl ( a ), 2‐thienyl ( b ), phenyl ( c )) have been prepared from octa‐1,7‐diyne‐substituted phosphaalkenes by utilizing the Fagan–Nugent route. The presence of two differently hybridized phosphorus centers (σ²,λ³ and σ³,λ³) in 5 offers the possibility to selectively tune the HOMO–LUMO gap of the compounds by utilizing the different reactivity of the two phosphorus heteroatoms. Oxidation of 5 a – c by sulfur proceeds exclusively at the σ³,λ³‐phosphorus atom, thus giving rise to the corresponding thioxophospholes 6 a – c . Similarly, 5 a is selectively coordinated by AuCl at the σ³,λ³‐phosphorus atom. Subsequent second AuCl coordination at the σ²,λ³‐phosphorus heteroatom results in a dimetallic species that is characterized by a gold–gold interaction that provokes a change in π conjugation. Spectroscopic, electrochemical, and theoretical investigations show that the phosphaalkene and the phosphole both have a sizable impact on the electronic properties of the compounds. The presence of the phosphaalkene unit induces a decrease of the HOMO–LUMO gap relative to reference phosphole‐containing π systems that lack a P?C substituent.     

Synthesis and spectral properties of mixedmeso-metallocenylporphyrins

A series of mixed porphyrins with different numbers of metallocenyl (ferrocenyl and cymantrenyl) and aryl (Ph and C₆F₅) groups at themeso-positions was obtained and characterized by¹H NMR, electronic absorption, and mass spectra. The downfield shift of NH signals as well as the bathochromic shift ofQ-bands can be attributed to a distortion of the porphyrin macrocycle upon the introduction of bulkymeso-substituents. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1045–1049, May, 1998.     

Boron Radical Cations from the Facile Oxidation of Electron‐Rich Diborenes

The realization of a phosphine‐stabilized diborene, Et₃P?(Mes)B?B(Mes)?PEt₃ ( 4 ), by KC₈ reduction of Et₃P?B₂Mes₂Br₂ in benzene enabled the evaluation and comparison of its electronic structure to the previously described NHC‐stabilized diborene IMe?(Dur)B?B(Dur)?IMe ( 1 ). Importantly, both species feature unusual electron‐rich boron centers. However, cyclic voltammetry, UV/Vis spectroscopy, and DFT calculations revealed a significant influence of the Lewis base on the reduction potential and absorption behavior of the B? B double bond system. Thus, the stronger σ‐donor strength and larger electronegativity of the NHC ligand results in an energetically higher‐lying HOMO, making 1 a stronger neutral reductant as 4 ( 1 : E_1/2=?1.55 V; 4 : ?1.05 V), and a smaller HOMO–LUMO gap of 1 accompanied by a noticeable red‐shift of its lowest‐energy absorption band with respect to 4 . Owing to the highly negative reduction potentials, 1 and 4 were easily oxidized to afford rare boron‐centered radical cations ( 5 and 6 ).     

Decorating Tetrathiafulvalene (TTF) with Fluorinated Phenyls through Sulfur Bridges: Facile Synthesis,Properties, and Aggregation through Fluorine Interactions

Tetrathiafulvalene derivatives ( TTF1 – TTF9 ) bearing fluorinated phenyl groups attached through the sulfur bridges have been synthesized by employing a copper‐mediated C–S coupling reaction of C₆H_5?xF_xI (x=1, 2, 5) and a zinc‐thiolate complex, (TBA)₂[Zn(DMIT)₂] (TBA=tetrabutyl ammonium, DMIT=1,3‐dithiole‐2‐thione‐4,5‐dithiolate), as the key step. Particularly, the selective synthesis of C₆F₅‐substituted ( TTF8 ) and C₆F₄‐fused ( TTF9 ) TTFs from C₆F₅I is disclosed. The physicochemical properties and crystal structures of these TTFs are fully investigated by UV/Vis absorption spectra, cyclic voltammetry, molecular orbital calculation, and single‐crystal X‐ray diffraction. The exchange of hydrogen versus fluorine on the peripheral phenyl groups show a notable influence on both the electronic and crystallographic natures of the resulting TTFs: 1) lowering both the HOMO and the LUMO energy levels, 2) modulating the electrochemical properties by regioselective and/or the degree of fluorination, 3) enhancing the driving forces of stacking by multiple fluorine interactions (F???S, C?F???π/π_F, C?F???F?C, and C?F???H). This work indicates that the decoration with fluorinated phenyls holds promise to produce functional TTFs with novel electronic and aggregation features.