Diphenylamino Groups Research Articles

Solid-state fluorescence properties and mechanofluorochromism of D–π-A pyridinium dyes bearing various counter anions

A pronounced bathochromic shift-type mechanofluorochromism (MFC) is found for D–π-A pyridinium dyes OD1–OD3 having diphenylamino group as an electron donor and pyridinium ring as an electron acceptor linked by carbazole as a π-conjugated bridge, and bearing various counter anions (X−=Cl−, Br−, or I−). Interestingly, both absorption and fluorescence peaks of as-recrystallized dyes show bathochromic shift by grinding, and the degrees of the bathochromic shift depend on the type of counter anion of OD1–OD3. We propose that the use of various counter anions for D–π-A pyridinium dyes can be one of the most effective strategies, not only to express a pronounced MFC, but also to control changes of fluorescence properties by the grinding and heating, resulting in fine-tuning of fluorescent color change by the MFC.

Highly efficient orange and white electrophosphorescence from solution-processible iridium(III) complexes

The luminescent properties of two cyclometalated iridium complexes containing 2-phenylbenzothiazole ligand were investigated. With diphenylamino groups in the ligands, these iridium complexes can form neat films by spin coating their solutions. It is also possible to prepare their doped films in small molecular host matrix N,N ′-dicarbazolyl-4,4′-biphenyl by spin coating. Partially solution-processed organic light-emitting diodes (OLEDs) were fabricated with a luminance efficiency of 20.18 cd A −1 (7.81%), which is even higher than the vacuum-deposited device data for these two complexes, and also better than those for other solution-processed iridium dopant/small molecular host systems. The two-element white OLEDs containing these orange phosphors and traditional blue-emitting iridium in N,N ′-dicarbazolyl-4,4′-biphenyl host also exhibited high efficiency of 12.39 cd A −1 . It is suggested that the incorporation of the diphenylamino substituents and thus the good hole-injecting and solution processing ability of these iridium complexes are responsible for the good performance. Two iridium complexes decorated by diphenylamino substituents in cyclometalating ligands are suitable for solution processing to fabricate monochromic and white organic light-emitting diodes, which exhibit even better performance than their vacuum-deposited devices or other solution-processed iridium phosphors/small molecular host systems. • The electrophosphorescence of two iridium complexes containing 2-phenylbenzothiazole ligands are studied. • The incorporation of arylamino groups in ligands makes these complexes solution-processible. • High-performance orange and white organic light-emitting diodes were realized with these iridium complexes as doped emitters.

An aggregation-induced emissive chromophore as a ratiometric fluorescent sensor for cyanide in aqueous media

A para-terphenyl derivative containing a lateral diphenylamino group and two terminal dicyanovinyl groups has been designed and synthesized. This compound displays aggregation-induced emission characteristics and thus shows intense intramolecular charge transfer fluorescence even in the condensed state, including in the aggregates formed in an aqueous solvent system consisting of greater than 99% water and in the solid state. The addition of cyanide to its aggregates in aqueous media induces a large blue shift in fluorescence, enabling ratiometric fluorescence sensing of cyanide anions. In addition, its prompt fluorescence responses to cyanide anions were also observed even in the solid state.

The effect of the diphenylamino side group on the reduction of the molecular interaction between polyurethane copolymer chains

Polyurethane (PU) with a diphenylamino side group is tested for low temperature flexibility at −30°C and compared with a linear PU without the diphenylamino side group. The PU is composed of 4,4′-methylenebis(phenylisocyanate) (MDI), poly(tetramethyleneglycol) (PTMG), 1,4-butanediol (BD), and the diphenylamino group that is grafted to PU chains by a second MDI. The mechanical and shape memory properties of these two types of PU, which differ in the PTMG and the diphenylamino group content, are compared. In the best case, a 306% increase in the maximum stress compared with the linear polymer is attained with a little decrease in the strain. Shape recovery at 45°C increases to 94% and remains ∼90% after four cyclic tests. Low temperature flexibility can be improved by increasing the diphenylamino content. The PU with a diphenylamino side group demonstrates the low temperature flexibility at −30°C, whereas the linear PU must be warmed to room temperature to attain the same degree of flexibility. The exceptional low temperature flexibility is analyzed and is discussed together with the experimental data. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013

P-Quaterphenyls Laterally Substituted with a Dimesitylboryl Group: A Promising Class of Solid-State Blue Emitters

A new family of p-quaterphenyls 1-6 laterally substituted with a bulky electron-accepting dimesitylboryl group has been designed and synthesized. These compounds were characterized by X-ray crystallography, UV-vis and fluorescence spectroscopy, and DFT calculations as well as thermogravimetric analysis (TGA), differential scanning calorimetry (DSC), and cyclic voltammetry (CV). X-ray single-crystal analysis revealed that the p-quaterphenyl main chain framework exhibits a twisted structure due to the steric effect of the lateral boryl group, and the intermolecular interactions are effectively suppressed in the solid state. Despite the significantly twisted main-chain structure, these molecules still display efficient intramolecular charge-transfer emissions with large Stokes shifts. An intriguing finding is that all these molecules show bright fluorescence with good to excellent quantum yields in the blue region in the solid state. In addition, the two representative p-quaterphenyls 3 and 4 containing both the electron-accepting boryl group and the electron-donating carbazolyl (3) or diphenylamino group (4) possess high thermal stability and good oxidation-reduction reversibility, which together with their excellent solid-state fluorescence efficiency make them promising bipolar transporting blue emitters.

Ethynyl-linked push–pull porphyrin hetero-dimers for near-IR dye-sensitized solar cells: photovoltaic performances versus excited-state dynamics

Ethynyl-linked porphyrin hetero-dimers substituted by a series of electron donors, namely, bis(4-methoxyphenyl)amino (BMPA), bis(4-tert-butylphenyl)amino (BTBPA) and 3,6-di-tert-butylcarbazol-9-yl (DTBC) as well as a reference dimer with a non-donor moiety (3,5-di-tert-butylphenyl, DTBP) have been synthesized to systematically investigate the influence of donor introduction on the photovoltaic performances of near-IR dye-sensitized solar cells (DSCs) with these sensitizers incorporated. Despite the expected bathochromic shift and intensification of long-wavelength absorption bands as well as elevated LUMO levels and thus increased electron injection driving forces, the substitution of diphenylamino groups (BMPA and BTBPA) with stronger electron-donating abilities gave rise to surprising mediocrity in the short-circuit photocurrent densities (J(sc)), leading to overall energy conversion efficiencies in the order BMPA (3.94%) < DTBP (4.57%) < BTBPA (4.83%) < DTBC (5.21%). A study of the in situ fluorescent behavior of these sensitizers revealed that for all the sensitizers, excited-state lifetimes were significantly shortened in the simulated DSC environment compared to those in a free solution. BMPA showed the shortest intrinsic in situ lifetime while DTBC showed the longest one. These results were correlated with the photovoltaic performances, which is required for a better understanding and further design of porphyrin array sensitizers.

Ph2N-Susbtituted Ethylene-Bridged p-Phenylene Oligomers: Synthesis and Photophysical and Redox Properties

For a series of p-phenylene-based oligomers terminated with two triphenylamines, their absorption, photoluminescence, and band gaps show a pattern of extensive π-conjugation with increasing array size. Oligomers with large central arrays have greater quantum yields than their small analogues. Cyclic voltammetric (CV) measurements indicated two-step oxidations of the two diphenylamino groups for compounds 1-5 and one-step oxidations for the two amines of large oligomers 6 and 7.

Highly solid-state emissive para-terphenyls laterally substituted with a diphenylamino group

Intense solid-state emissions with good to excellent quantum yields were achieved through the introduction of bulky electron-donating diphenylamino groups at the side positions of an electron-accepting para-terphenyl framework.

Synthesis and optical properties of novel pyrido[1,2-a]benzimidazole-containing 1,3,4-oxadiazole derivatives

A series of novel substituted 1,3,4-oxadiazole derivatives containing pyrido[1,2-a]benzimidazole moiety were synthesized and characterized using FTIR, 1H NMR, 13C NMR, and HRMS. An efficient tandem reaction was employed as a key step in constructing the pyrido[1,2-a]benzimidazole moiety under very mild condition. The structure of compound 4a was established by X-ray crystallography. The UV–vis absorption and fluorescence spectral characteristics of these compounds were investigated in several solvents. Compounds 4a–i display similar absorptions, with absorption peaks ranging from 330 to 339nm in acetonitrile, while the absorption maxima of compound 4j bearing a diphenylamino group on the benzene ring is red-shifted distinctly to 377nm due to the strong electron-donating property of its substituent and extended π-conjugated system. All these target heterocyclic compounds present blue-green emissions (461–487nm) in dilute solutions and show high quantum yields of fluorescence (ФPL=0.65−0.99) in dichloromethane.

Synthesis and Photophysical Properties of 2-Donor-7-acceptor-9-silafluorenes: Remarkable Fluorescence Solvatochromism and Highly Efficient Fluorescence in Doped Polymer Films

Recently, π-conjugated molecules containing a 9-silafluorene moiety have attracted considerable attention owing to their potential applications in organic electronics. While most studies focus on the oligomers and (co)polymers of 9-silafluorenes, functionalized 9-silafluorenes themselves remain unexplored. In this paper, we describe the preparation, photophysical properties, and theoretical calculations of 2-amino-7-acceptor-9-silafluorenes and we show that these silafluorenes can potentially be used as novel chromophores for functional organic materials. The D-π-A type silafluorenes were prepared by Pd-catalyzed intramolecular coupling of 2-(3-aminophenyldiisopropylsilyl)aryl triflates and the subsequent functional group conversion through reduction of the cyano group to a formyl and Knoevenagel condensation of the formyl group with malonitrile. The UV−visible absorption and fluorescence spectra of the D-π-A type silafluorenes exhibited a red-shift when the electron-withdrawing nature of the acceptor increased. The emission maxima of the fluorescence were highly dependent on the solvent. In the cases of formyl- and dicyanoethenyl-substituted silafluorenes, the emission colors ranged from blue to yellow for the formyl derivatives and from green to red for the dicyanoethenyl derivatives. The noticeable fluorescence solvatochromism suggests the intramolecular charge-transfer character of the excited states. The silafluorenes also exhibited fluorescence in the solid state (e.g., a neat thin film and a doped polymer film), and the emission color was dependent on the polarity of the polymer. In the solid state, the quantum yields of diphenylamino derivatives were generally higher than those of dimethylamino derivatives, presumably because the bulky diphenylamino group prevented chromophores from assembling close to each other. A comparison of the photophysical properties and theoretical calculations of D-π-A type silafluorenes with those of the corresponding fluorenes revealed that the silicon bridge contributed to the extension of the effective conjugation length of the biphenyl moiety when the acceptor was either hydrogen, trifluoromethyl, or a cyano group, whereas there was no contribution of the silicon bridge to the π-extension in silafluorenes substituted by strong electron acceptors such as formyl and dicyanoethenyl groups. White photoluminescence was demonstrated with an excellent quantum yield of 0.81 in the solid state from the poly(methyl methacrylate) (PMMA) film doped with Ph2N/CHO- and Ph2N/CH═(CN)2-substituted silafluorenes. This work reveals the potential of D-π-A type silafluorenes as versatile organic emitting materials.

Electrochemistry and Electrogenerated Chemiluminescence of a Novel Donor−Acceptor FPhSPFN Red Fluorophore

We report here the electrogenerated chemiluminescence (ECL) of a red fluorophore diphenylaminospirobifluorenylfumaronitrile (FPhSPFN). FPhSPFN contains two diphenylamino groups as strong electron donors at the ends linked through a nonplanar bulky spirobifluorene linker to a common fumaronitrile group as a strong electron acceptor. The cyclic voltammetry of this compound shows two one-electron transfer reduction waves and one single overall two-electron oxidation wave consisting of closely spaced waves with a peak separation of 63 mV. Chronoamperometry with an ultramicroelectrode (UME) confirmed that each reduction wave involves a 1e transfer and that the oxidation wave contains an overall 2e transfer. The first reduction wave is Nernstian, Eo1,red = −1.09 V versus SCE, and the second reduction wave, Eo2,red = −1.50 V versus SCE, produces a film on the electrode. By comparison to a digital simulation, the oxidation is assigned to two reversible, closely spaced, one-electron processes for oxidation with Eo...

Intensely Fluorescent Azobenzenes: Synthesis, Crystal Structures, Effects of Substituents, and Application to Fluorescent Vital Stain

2-[Bis(pentafluorophenyl)boryl]azobenzenes bearing hydrogen, methoxy, dimethylamino, trifluoromethyl, fluoro, n-butyl, and tert-butyldimethylsiloxy groups at the 4'-position or methoxy and bromo groups at the 4-position have been synthesized. The 4-bromo group of the 2-boryl-4-bromoazobenzene derivative was converted to phenyl and diphenylamino groups by palladium-catalyzed reactions. The absorption and fluorescence properties have been investigated using UV/Vis and fluorescence spectroscopy. The 2-borylazobenzenes emitted an intense green, yellow, and orange fluorescence, in marked contrast to the usual azobenzene fluorescence. The 4'-siloxy derivative showed the highest fluorescence quantum yield (0.90) among those reported for azobenzenes to date. The correlation between the substituent and the fluorescence properties was elucidated by studying the effect of the substituent on the relaxation process and from DFT and TD-DFT calculations. An electron-donating group at the 4'-position was found to be important for an intense emission. Application of fluorescent azobenzenes as a fluorescent vital stain for the visualization of living tissues was also investigated by microinjection into Xenopus embryos, suggesting these compounds are nontoxic towards embryos.

Aromatic Fumaronitrile Core-Based Donor−Linker−Acceptor−Linker−Donor (D-π-A-π-D) Compounds: Synthesis and Photophysical Properties

A new class of aromatic fumaronitrile core-based compounds with different donors and linkers has been synthesized and well characterized. Compounds 1 and 2 have indole and 2-phenylindole groups as electron donors, respectively. Compounds 3 and 4 have a diphenylamino group as the electron donor, and compound 5 has a 3,6-di-tert-butylcarbazole group as an electron donor. These compounds absorb in the blue-to-green region and emit in the blue-to-red region depending on the electron donor, linker, and solvents. The quantum yields of fluorescence of these compounds in solution are measured and found to be moderate, but in solid states, they are high. These compounds display strong emission solvatochromism that is reflected by a large shift in their fluorescence emission maxima on changing the solvents. This change is accompanied by a successive decrease in fluorescence intensity. The fluorescence lifetimes of these compounds are measured in different solvent and found to vary from <1 to 7 ns. Optical switching of these compounds with solvents, concentration, and excitation energy have been studied. The correlation between the functional group and optical properties has been established to some extent. The ability of these compounds to function as colorimetric and luminescence pH sensors is demonstrated with color changes and luminescence switching upon the addition of trifluoroacetic acid. The potentiality of these compounds for application in optoelectronics has been optically assessed.

Contrasting Solvent Polarity Effect on the Photophysical Properties of Two Newly Synthesized Aminostyryl Dyes in the Lower and in the Higher Solvent Polarity Regions

Solvent polarity effect on the photophysical properties of two newly synthesized aminostyryl-thiazoloquinoxaline dyes, one with a flexible diphenylamino group, namely, N,N-diphenyl-4-[2-(thiazolo[4,5-b]quinoxalin-2-yl)vinyl]aniline (TQ1), and the other with a rigid julolidinylamino group, namely, (9-[2-(thiazolo[4,5-b]quinoxalin-2-yl)vinyl]julolidine) (TQ2), have been investigated in different aprotic solvents and solvent mixtures. From the polarity dependent changes in the absorption and fluorescence spectral properties, it is indicated that the fluorescent states of the dyes are of intramolecular charge transfer (ICT) character. For both the dyes, the photophysical properties like fluorescence quantum yields (Phi(f)), fluorescence lifetimes (tau(f)), radiative rate constants (k(f) = Phi(f)/tau(f)), and nonradiative rate constants (k(nr) = 1/tau(f) - Phi(f)/tau(f)) show clearly contrasting solvent polarity effects in the lower and in the higher solvent polarity region, causing an interesting reversal in the properties below and above an intermediate solvent polarity. It is inferred that the domination of the cis-trans isomerization in the lower solvent polarity region and that of the twisted intramolecular charge transfer (TICT) state formation in the higher solvent polarity region are responsible for the observed contrasting solvent polarity effects on the photophysical properties of the two dyes. As both isomerization and TICT state formation causes an enhancement in the nonradiative decay rate of the excited dyes and both the processes become less significant at the intermediate solvent polarity region, the two dyes show their largest Phi(f) and tau(f) values at intermediate solvent polarities. Suitable mechanistic schemes have been proposed and qualitative potential energy diagrams have been presented to explain the observed results with the changes in the polarity of the solvents used.

Organic Thin-Film Solar Cells Using Electron-Donating Perylene Tetracarboxylic Acid Derivatives

Various electron-donating amino groups were introduced into the perylene core of perylene tetracarboxylic acid derivatives (PTCs) to address the potential use in organic solar cells. Broad absorptions of the PTC solutions in the visible to near-infrared (NIR) region suggest that PTCs are promising light-harvesting molecules for solar cells. Electrochemical measurements reveal that the introduction of the electron-donating amino groups makes the energy level of the highest occupied molecular orbital (HOMO) shallow, imparting electron-rich characteristics to the PTCs. The electronic properties of the PTCs are studied on the basis of quantum chemical calculations. The results show that the variation of the amino groups has a significant influence on the HOMO level, while the lowest unoccupied molecular orbital (LUMO) level is relatively sensitive to the electronegativity of the PTC terminal atoms. The PTC thin films exhibit broad absorption bands in the visible to NIR region, as for the PTC solutions, and possess relatively shallow HOMO and LUMO energies that are higher or comparable to those of fullerene C60. These excellent properties encouraged us to employ amine-substituted PTCs as electron donors in a thin film solar cell with C60 as an n-type semiconductor. Photovoltaic devices with a structure of indium tin oxide (ITO)/PTCs/C60/bathocuproine (BCP)/Al were fabricated by spin-coating PTCs on an ITO electrode. The devices with perylene tetracarboxylic acid diimides (PTCDIs), bearing highly basic amino groups (Py-PTCDI, Me2N-PTCDI, and Ph2N-PTCDI), exhibit the higher power conversion efficiencies than those with carbazoyl PTCDI (Cz-PTCDI) and perylene tetracarboxylic acid dianhydrides (PTCDAs). The higher device performance originates from the efficient electron transfer from the PTCs to C60 as the results of the relatively shallow HOMO and LUMO levels of the PTCs bearing the highly basic amino groups. The dependence of the device performance on the PTC film thickness indicates that the introduction of diphenylamino groups on the perylene core suppresses the nonradiative decay of the exciton without decreasing the hole mobility. These results will provide important information for the molecular design of post PTC derivatives.

Synthesis and Properties of a Novel Cross-Linked Electroactive Polymer Formed from a Bipolar Starburst Monomer

This Article describes the synthesis and physical properties of two bipolar starburst monomers: 1,3,5-tris{5-(7-(carbazol-9-yl)-(9,9′-spirobifluoren-2-yl)-1,3,4-oxadiazol-2-yl}benzene (OXD-CBZ) and 1,3,5-tris[7-diphenyl-(9,9′-spirobifluorene)-1,3,4-oxadiazoyl]benzene (OXD-DPA) featuring an electron-deficient tris(1,3,4-oxadiazole)phenylene ring as an interior core bridged by rigid spirobifluorene units to terminal electroactive carbazole (CBZ) and diphenylamino (DPA) groups. The electronic absorption spectra of OXD-CBZ and OXD-DPA depend only slightly on the solvent polarity, revealing that weak electronic coupling existed between the donor (CBZ and diphenylamino groups) and acceptor (1,3,4-oxadiazole) moieties in the ground state. In contrast, the emission spectra of these starburst bipolar molecules were strongly dependent on the solvent polarity, a phenomenon that we attribute to the polarized excited states generated through intramolecular charge transfer. The starburst monomer OXD-CBZ exhibited a redox gradient, where the peripheral CBZ moieties exhibited lower oxidation potentials than those of the fluorene units in the interior, allowing us to obtain a new electropolymerized macromolecule. The polymer films derived from OXD-CBZ exhibited good conductivity, reversible electrochemical processes, and stable color changes (from transparent to green to light blue) with high coloration efficiency upon electro-oxidation. The radical cations of OXD-CBZ were localized within the CBZ rings; the lack of substituents at the C3 and C6 positions of the CBZ unit led to the effective electrochemical cross-linking process. In contrast, electro-oxidation of OXD-DPA, which was end-capped with DPA groups, produced stable radical cations that did not undergo associated electrochemical reactions. The higher stability of the OXD-DPA radical cations through resonance stabilization with the fluorene ring impeded the progress of typical triphenylamine dimerization reactions.

Screening Electronic Communication through ortho‐, meta‐ and para‐Substituted Linkers Separating Subphthalocyanines and C60

We have prepared two complementary series of SubPc-C(60) (SubPc=subphthalocyanine) electron/energy donor-acceptor systems, in which the two constituents are linked through ortho-, meta-, or para-substituted phenoxy spacers. In one of the series (1 a) the SubPc units bear iodine atoms, while in the other series (1 b) diphenylamino groups are linked to the SubPc macrocycles. The iodine atoms and diphenylamino groups both influence the resulting oxidation potentials of the electron-donating SubPc. They also modulate the outcome of excited state interactions, namely, energy and/or charge transfer. In addition, we have studied the impact that the substitution pattern in the phenoxy spacer exerts onto intramolecular processes in the ground and excited states. Although some of these processes are governed by the spatial separation between both components, the different electronic coupling through ortho-, meta-, or para- connections also plays decisive roles in some cases.

Synthesis of Poly(N‐aryl‐2,7‐carbazole)s for Efficient Blue Electroluminescence Materials

AbstractSeveral poly(N‐phenyl‐2,7‐carbazole)s that have dialkoxy groups at the m‐ and p‐positions (PmpCzDC, PmpPhDC, PmpCBiDC, PmpEHC), a silyl group at the p‐position (PpPhDSiC), and a diphenylamino group (PmPhDAC, PmEHAC) at the m‐position of the N‐phenyl portion are synthesized, and their optical properties are characterized. These polymers have been used as emitting layer materials of organic light‐emitting diode (OLED) devices that have a configuration of ITO/PEDOT(PSS)/polymer/CsF/Al. The OLED devices embedded with PmpCzDC, PmpPhDC, and PmpEHC show intense luminance of about 15 000 cd · m−2 with efficiencies of about 1 cd · A−1, while the devices embedded with PpPhDSiC, PmPhDAC, and PmEHAC show less luminance but retain the color purity of blue emission under a wide range of applied voltages.magnified image

Hole Mobilities of 2,7- and 2,2′-Disubstituted 9,9′-Spirobifluorene-Based Triaryldiamines and Their Application as Hole Transport Materials in OLEDs

Hole mobilities of up to 2 × 10−3 cm2 V−1 s−1 of 2,7- and 2,2′-disubstituted spirobifluorene-based triaryldiamine derivatives have been measured using time-of-flight (TOF) techniques. Among these derivatives, 27DPSF (possessing diphenylamino groups attached onto the same biphenyl branch of spirobifluorene) and 22DPASF (possessing extended π-conjugation of the chromophore) exhibited the highest hole mobilities because of their greater intermolecular interactions. The charge transport parameters were extracted, using a Gaussian disorder model (GDM), from detailed temperature- and field-dependent hole mobility measurements. For 2,2′-disubstituted systems possessing different diarylamino groups, the hole mobilities decreased in the order 22DPSF > 22DTSF > 22DBPSF, indicating that spatial hindrance had a crucial effect on the hole transport behavior. To verify these disubstituted spirobifluorene-based amines can be used as HTLs in OLED devices. A standard device was fabricated with the configuration ITO/m-MTDA...

Alternative Synthesis of C60‐Diphenylaminofluorene Derivatives for Nonlinear Photonic Applications: Method of Preparation and Characterization

An alternative synthetic route for the preparation of key intermediate synthons 7‐α‐bromoacetyl‐2‐diphenylaminofluorene (α‐BrDPAF‐H) and 7‐α‐bromoacetyl‐9,9‐dialkyl‐2‐diphenylaminofluorene (α‐BrDPAF‐Cn) was demonstrated. The latter reactions involved the first step of dialkylation of 2‐bromofluorene at C9 position of the fluorene moiety, the second step of a diphenylamino group attachment at C2 position of the resulting dialkylfluorene, and the third step of Friedel‐Craft acylation of α‐bromoacetyl group at C7 position of dialkylated diphenylaminofluorene. From the intermediates α‐BrDPAF‐H and α‐BrDPAF‐Cn, a series of C60‐keto‐DPAF nanostructures, such as the fullerene monoadducts C60(>DPAF‐H) and C60(>DPAF‐Cn), where n is 2, 4, or 10, were synthesized in a reasonable yield. Molecular mass ions of the dyads C60(>DPAF‐H), C60(>DPAF‐C2), C60(>DPAF‐C4), and C60(>DPAF‐C10) were clearly detected in positive ion matrix‐assisted laser desorption ionization mass spectrum (MALDI–MS) that confirmed the composition mass of each compound synthesized.