Photomechanochemistry: harnessing mechanical forces to enhance photochemical reactions

• Francesco Mele,
• Ana M. Constantin,
• Andrea Porcheddu,
• Raimondo Maggi,
• Giovanni Maestri,
• Nicola Della Ca’ and
• Luca Capaldo

Beilstein J. Org. Chem. 2025, 21, 458–472, doi:10.3762/bjoc.21.33

• photomechanochemical reactor where the jar of the ball mill vibrates within an aluminum frame on which UV-C LEDs are mounted. The milling vessel used in this process is a cylinder of quartz glass with PFA (perfluoroalkoxyalkane) caps on both ends to absorb impacts. Thus, the Mallory reaction to get triphenylene was

Efficient synthesis of fluorinated triphenylenes with enhanced arene–perfluoroarene interactions in columnar mesophases

• Yang Chen,
• Jiao He,
• Hang Lin,
• Hai-Feng Wang,
• Ping Hu,
• Bi-Qin Wang,
• Ke-Qing Zhao and
• Bertrand Donnio

Beilstein J. Org. Chem. 2024, 20, 3263–3273, doi:10.3762/bjoc.20.270

• chains and derived from the classical triphenylene core self-assembling in columnar mesophases based on this paradigm. These mesogenic compounds were simply obtained in good yields by the nucleophilic substitution (SNFAr) of various types of commercially available fluoroarenes with the electrophilic

• derivatives and the antiparallel stacking mode into columnar structures stabilized by arene–perfluoroarene intermolecular interactions were confirmed by the single-crystal structure of the alkoxy-free side chain analog, i.e., 1,2,4-trifluoro-3-(perfluorophenyl)triphenylene (F). UV–vis absorption and

• red-shift of the emission peak. Keywords: arene–perfluoroarene interaction; decafluorobiphenyl; fluorinated triphenylene; fluoroarene nucleophilic substitution; organolithium; Introduction Non-covalent arene–fluoroarene intermolecular interactions [1][2] are drawing increasing attention due to their

Surprising acidity for the methylene of 1,3-indenocorannulenes?

• Shi Liu,
• Märt Lõkov,
• Sofja Tshepelevitsh,
• Ivo Leito,
• Kim K. Baldridge and
• Jay S. Siegel

Beilstein J. Org. Chem. 2024, 20, 3144–3150, doi:10.3762/bjoc.20.260

• conformationally planar-locked 2,3-diphenylindene (pKa 17.7 in DMSO [17]. The CL perspective also allows one to create graphs with points representing the aromatic elements, such as, benzene, Cp anion, pyrrole, etc. (Scheme 2, top). Triphenylene is a simple cyclic graph of three benzene elements and their direct

• connections. A simple modification of the triphenylene graph is the replacement of benzene by Cp anion (Scheme 2, middle). From the CL graph perspective, the anion of cyclopentaphenanthrene is related to that of dibenzofluorene the same way as the Cp anion is related to that of indene. Therefore

• ); triphenylene above cyclopentaphenanthrene (right); [lower] as with middle but dibenzofluorene (left) and fluorenocorannulene (right). CL graph perspective on acidic PAH-CpHs; pentabenzocorannulene and pentabenzoazocorannulene (upper); phenyltetrabenzofluorene and tetrabenzofluorene TBF (lower). Relative

Switchable molecular tweezers: design and applications

• Pablo Msellem,
• Maksym Dekthiarenko,
• Nihal Hadj Seyd and
• Guillaume Vives

Beilstein J. Org. Chem. 2024, 20, 504–539, doi:10.3762/bjoc.20.45

• acridinium is that it can undergo the addition of a nucleophile like HO− or RO− forming an acridane derivative having non-planar geometry and different electronic properties. Triphenylene tweezers 6 are able to intercalate planar electron-rich guest molecules like TTF and pyrene. Upon the addition of a

Synthesis of π-conjugated polycyclic compounds by late-stage extrusion of chalcogen fragments

• Aissam Okba,
• Pablo Simón Marqués,
• Kyohei Matsuo,
• Naoki Aratani,
• Hiroko Yamada,
• Gwénaël Rapenne and
• Claire Kammerer

Beilstein J. Org. Chem. 2024, 20, 287–305, doi:10.3762/bjoc.20.30

• dithienonaphthalene products (e.g., 16) exhibit very different fluorescence properties, S-extrusion from thiophene-annelated thiepines was consequently exploited for peroxide sensing. Very recently, Zhou et al. reported the synthesis of S-doped phenanthrene and triphenylene derivatives via the thermally-induced ring

• -doped triphenylene derivative 22. In the same year, An et al. reported their investigations regarding chalcogen-doped hexa-peri-benzocoronene (HBC) derivatives and their controllable conversion into hydrocarbon nanographenes by ring contraction of the heteropine moiety [65]. The authors first tackled

• dithienonaphthalenes, upon S-extrusion triggered by electrochemical oxidation. Bottom: Exploitation of the S-extrusion process for peroxide sensing, taking advantage of the lability of oxidized dithienobenzothiepine to generate highly fluorescent dithienonaphthalene [63]. Synthesis of S-doped extended triphenylene

Charge carrier transport in perylene-based and pyrene-based columnar liquid crystals

• Alessandro L. Alves,
• Simone V. Bernardino,
• Carlos H. Stadtlober,
• Edivandro Girotto,
• Giliandro Farias,
• Rodney M. do Nascimento,
• Sergio F. Curcio,
• Thiago Cazati,
• Marta E. R. Dotto,
• Juliana Eccher,
• Leonardo N. Furini,
• Hugo Gallardo,
• Harald Bock and
• Ivan H. Bechtold

Beilstein J. Org. Chem. 2023, 19, 1755–1765, doi:10.3762/bjoc.19.128

• the charge carrier mobility (parallel vs perpendicular to the columnar axis) of up to ten orders of magnitude [3][4][5][6][7]. In 1994, Adam and collaborators obtained a hole-mobility of up to 0.1 cm2 V−1 s−1 for a triphenylene-based columnar liquid crystal [8], motivating intense research activity to

Palladium-catalyzed solid-state borylation of aryl halides using mechanochemistry

• Koji Kubota,
• Emiru Baba,
• Tamae Seo,
• Tatsuo Ishiyama and
• Hajime Ito

Beilstein J. Org. Chem. 2022, 18, 855–862, doi:10.3762/bjoc.18.86

• bearing relatively large conjugated structures (1f−m) tended to show low reactivity under the optimized conditions at 60 °C, but the reactions proceeded smoothly at 110 °C. For example, the bromo-substituted triphenylamine (1f), pyrene (1g and 1h), fluoranthene (1i), biphenyl (1j), triphenylene (1k

Synthetic approaches to bowl-shaped π-conjugated sumanene and its congeners

• Shakeel Alvi and
• Rashid Ali

Beilstein J. Org. Chem. 2020, 16, 2212–2259, doi:10.3762/bjoc.16.186

• ’ “Suman”, which means “Sunflower”), a beautifully simple yet much effective bowl-shaped C3-symmetric polycyclic aromatic hydrocarbon having three benzylic positions clipped between three phenyl rings in the triphenylene framework has attracted a tremendous attention of researchers worldwide. Therefore

• sumanene (2), it is not only gifted with three benzylic positions stapled between the benzene rings of the triphenylene system but also possess the bowl-curvature which enables stereoselective functionalization at these valuable positions. Taking the advantage of these benzylic positions, two years later

• -workers attempted to synthesize trithiasumanene 151 [72] from triphenylene 139 but they could obtain merely mono- and di-bridged systems and no required product was observed (Scheme 38) [73]. However, the group of Otsubo in 1999 provides the breakthrough by successfully synthesizing the first member of

Synthesis of triphenylene-fused phosphole oxides via C–H functionalizations

• Md. Shafiqur Rahman and
• Naohiko Yoshikai

Beilstein J. Org. Chem. 2020, 16, 524–529, doi:10.3762/bjoc.16.48

• Md. Shafiqur Rahman Naohiko Yoshikai Division of Chemistry and Biological Chemistry, School of Physical and Mathematical Sciences, Nanyang Technological University, Singapore 637371, Singapore 10.3762/bjoc.16.48 Abstract The synthesis of triphenylene-fused phosphole oxides has been achieved

• via 1,4-cobalt migration. The resulting 7-hydroxybenzo[b]phosphole derivative was used for further π-extension through Suzuki–Miyaura couplings and a Scholl reaction, the latter closing the triphenylene ring. The absorption and emission spectra of the thus-synthesized compounds illustrated their

• nature as hybrids of triphenylene and benzo[b]phosphole. Keywords: C–H functionalization; fluorescence; phosphole; polycyclic aromatic hydrocarbons; triphenylene; Introduction The phosphorus-containing five-membered ring, phosphole, has attracted significant attention as a structural motif in π

Nanopatterns of arylene–alkynylene squares on graphite: self-sorting and intercalation

• Tristan J. Keller,
• Joshua Bahr,
• Kristin Gratzfeld,
• Nina Schönfelder,
• Marcin A. Majewski,
• Marcin Stępień,
• Sigurd Höger and
• Stefan-S. Jester

Beilstein J. Org. Chem. 2019, 15, 1848–1855, doi:10.3762/bjoc.15.180

• solvent molecules are sometimes resolved as intercalation adducts in STM of self-assembled monolayers. On the other hand, reports on intercalated TCB molecules are rather rare. Two exceptions are the observations of TCB in monolayers of arylene–alkynylene pentagons as well as triphenylene/azobenzene-based

Triphenylene discotic liquid crystal trimers synthesized by Co₂(CO)₈-catalyzed terminal alkyne [2 + 2 + 2] cycloaddition

• Bin Han,
• Ping Hu,
• Bi-Qin Wang,
• Carl Redshaw and
• Ke-Qing Zhao

Beilstein J. Org. Chem. 2013, 9, 2852–2861, doi:10.3762/bjoc.9.321

• trimers using Co2(CO)8-catalyzed terminal alkyne [2 + 2 + 2] cycloaddition reaction is reported. The trimers consist of three triphenylene discotic units linked to a central 1,2,4-trisubstituted benzene ring via flexible spacers. The trimers were synthesized in the yields up to 70% by mixing the monomers

• exhibited a rectangular columnar mesophase, while 5b and 5c possessing an ether linkage and a shorter spacer display a hexagonal columnar mesophase. The connecting functional group and the length of the flexible spacer between the central benzene ring and the triphenylene units have pivotal influence on the

• mesomorphism. Keywords: Co2(CO)8 catalyzed cycloaddition; columnar mesophase; discotic liquid crystal; triphenylene; oligomer; Introduction Discotic liquid crystals (DLCs) with nematic phase have been commercially utilized in the liquid crystal display industry as optical compensating films for widening the

Novel supramolecular affinity materials based on (−)-isosteviol as molecular templates

• Christina Lohoelter,
• Malte Brutschy,
• Daniel Lubczyk and
• Siegfried R. Waldvogel

Beilstein J. Org. Chem. 2013, 9, 2821–2833, doi:10.3762/bjoc.9.317

• particular as templates for tracing air-borne arenes at low concentration. The affinities of the synthesized materials towards different air-borne arenes were determined by 200 MHz quartz crystal microbalances. Keywords: affinity materials; (−)-Isosteviol; supramolecular chemistry; triphenylene ketals

• ][6][7][8][9][10]. Particular interest was given to C3-symmetric structures, serving e.g. as templates in asymmetric catalysis or molecular recognition [11][12][13][14]. A specific but potent subclass of such C3-symmetric architectures is represented by triphenylene ketals [15]. They have found

• [38][39], Within in a nine-step synthesis triphenylene ketals based on (−)-isosteviol were prepared [40]. Receptor structures 2 equipped with amino or sulfonylamido functionalities were obtained (Figure 2). In addition to triphenylene ketals, triptycene-based structures also exhibit the geometrical

Homolytic substitution at phosphorus for C–P bond formation in organic synthesis

• Hideki Yorimitsu

Beilstein J. Org. Chem. 2013, 9, 1269–1277, doi:10.3762/bjoc.9.143

• )-bridged biphenyls (Scheme 20) [46]. Subsequently, Liu reported an efficient synthesis of bis(phosphoryl)-bridged ladder triphenylene by means of the radical clipping with (Me3Sn)2PPh (Scheme 21) [47]. In light of the increasing importance of phosphoryl-bridged π-conjugated skeletons in organic material

• )-bridged ladder triphenylene by radical phosphination. Photoinduced phosphination of perfluoroalkyl iodides with tetraphenyldiphosphine. Ti(III)-mediated radical phosphination of organic bromides with white phosphorus. Radical anti-selective diphosphination of terminal alkynes. Photoinduced radical

Synthesis and structure of trans-bis(1,4-dimesityl-3-methyl-1,2,3-triazol-5-ylidene)palladium(II) dichloride and diacetate. Suzuki–Miyaura coupling of polybromoarenes with high catalytic turnover efficiencies

• Jeelani Basha Shaik,
• Venkatachalam Ramkumar,
• Babu Varghese and
• Sethuraman Sankararaman

Beilstein J. Org. Chem. 2013, 9, 698–704, doi:10.3762/bjoc.9.79

• polychloroarenes did not give a clean reaction, and the reactions were sluggish in comparison to polybromoarenes. In addition, unlike the polybromo derivatives, the polychloroarene derivatives of pyrene, triphenylene and [2,2]paracyclophane are not readily available. Conclusion In conclusion, the dichloro complex

• ); 13C NMR (125 MHz, CDCl3) δ 144.3, 136.4, 131.0, 130.0 (q, J = 31.8 Hz), 129.4, 128.5, 125.9, 125.7, 125.6 (q, J = 2.5 Hz), 124.4 (q, J = 270 Hz); HRMS (ESI–QTOF): m/z calcd for C44H23F12 779.1608, found 779.1616. 2,3,6,7,10,11-Hexakis(4-trifluoromethylphenyl)triphenylene (25): Prepared from

Efficient electroorganic synthesis of 2,3,6,7,10,11-hexahydroxytriphenylene derivatives

• Carolin Regenbrecht and
• Siegfried R. Waldvogel

Beilstein J. Org. Chem. 2012, 8, 1721–1724, doi:10.3762/bjoc.8.196

• . Precipitation during electrolysis avoided over-oxidation of the electron-rich triphenylene derivatives [12]. Yields up to 62% were obtained when tetrabutylammonium tetrafluoroborate (TBABF4) in acetonitrile (ACN) was used as electrolyte [11]. To our delight, we found that the electrolysis is accomplished under

• Anodic oxidation of catechol ketals We report a simple protocol for the anodic oxidation of catechol ketals forming triphenylene ketals (Scheme 1). Best results were obtained in PC and TMABF4 (method A) or TBABF4 (method B) as electrolytes. Performing the reaction in PC is beneficial for several reasons

• : PC is hazard-free, inexpensive and suitable for large-scale reaction. Moreover, triphenylene ketals have lower oxidation potentials than the corresponding catechol ketals. Since the non-polar products exhibit a relative poor solubility in PC, precipitation is achieved during the electrolysis. Usually

Liquid-crystalline nanoparticles: Hybrid design and mesophase structures

• Gareth L. Nealon,
• Romain Greget,
• Cristina Dominguez,
• Zsuzsanna T. Nagy,
• Daniel Guillon,
• Jean-Louis Gallani and
• Bertrand Donnio

Beilstein J. Org. Chem. 2012, 8, 349–370, doi:10.3762/bjoc.8.39

• diameter coated with triphenylene based mesogenic thiols 236,6 (Figure 25) were prepared by using the direct method to give a surface exclusively coated with the discotic ligands [93]. These materials did not display mesomorphism in the neat state, but were readily dispersed into the columnar phase of

• triphenylene discotic liquid crystals without disruption of the nature of the mesophase. Furthermore, thin films of Au@236,6 displayed 2-D hexagonal ordering on TEM grids, with interparticle distances less than twice the length of the organic moieties suggesting that the ligands at the surface were

Donor-acceptor substituted phenylethynyltriphenylenes – excited state intramolecular charge transfer, solvatochromic absorption and fluorescence emission

• Ritesh Nandy and
• Sethuraman Sankararaman

Beilstein J. Org. Chem. 2010, 6, 992–1001, doi:10.3762/bjoc.6.112

• Ritesh Nandy Sethuraman Sankararaman Department of Chemistry, Indian Institute of Technology Madras, Chennai 600036, India 10.3762/bjoc.6.112 Abstract Several 2-(phenylethynyl)triphenylene derivatives bearing electron donor and acceptor substituents on the phenyl rings have been synthesized. The

• . These results indicate that the fluorescence emission arises from excited state intramolecular charge transfer in these molecules where the triphenylene chromophore acts either as a donor or as an acceptor depending upon the nature of the substituent on the phenyl ring. HOMO–LUMO energy gaps have been

• estimated from the electrochemical and spectral data for these derivatives. The HOMO and LUMO surfaces were obtained from DFT calculations. Keywords: charge transfer; fluorescence; solvatochromism; solvent effect; triphenylene; Introduction Fluorescent molecular probes that emit in the visible region and

Novel banana-discotic hybrid architectures

• Hari Krishna Bisoyi,
• H. T. Srinivasa and
• Sandeep Kumar

Beilstein J. Org. Chem. 2009, 5, No. 52, doi:10.3762/bjoc.5.52

• crystalline property probably because of the incompatibility of the bent-core with the discotic core. Keywords: bent-core; dimer; discotic; triphenylene; Introduction Liquid crystals are unique functional self-organized soft materials which possess order and dynamics. Recently, banana liquid crystals or

• in mind, we have designed and synthesized novel banana-discotic dimers. A typical five-ring banana liquid crystal and triphenylene based discotic [27] liquid crystals were chosen to prepare these novel dimers. Here we report the synthesis, characterization and phase behavior of these novel dimers

• two dimensional lattices. The synthesis of the target compounds, banana-bridged discotic dimer 6 and banana-discotic dimers 8a and 8b are shown in Scheme 1 and Scheme 2, respectively. In compound 6 a five-ring banana unit joins two triphenylene discotic cores via two flexible alkyl spacers whereas in