Ionic Charge-Transfer Liquid Crystals Formed by Alternating Supramolecular Copolymerization of Liquid π-Donors and TCNQ

A new family of liquid π-donors, lipophilic dihydrophenazine (DHP) derivatives, show remarkably high π-electron-donor property which exhibit supramolecular alternating copolymerization with 7,7,8,8-tetracyanoquinodimethane (TCNQ), giving ionic charge-transfer (ICT) complexes. The ICT complexes form distinct columnar liquid crystalline (LC) mesophases with well-defined alternating molecular alignment as demonstrated by UV-Vis-NIR spectra, IR spectra, and X-ray diffraction (XRD) patterns. These liquid crystalline ICT complexes display unique phase transitions in response to mechanical stress: the columnar ICT phase is converted to macroscopically oriented smectic-like mesophases upon applying shear force. Although there exist reports on the formation of ICT in the crystalline state, this study provides the first rational identification of ICT mesophases based on the spectroscopic and structural data. The liquid crystalline ICT phases are generated by strong electronic interactions between the liquid π-donors and solid acceptors. It clearly shows the significance of simultaneous fulfillment of strong π-donating ability and ordered self-assembly of the stable ICT pairs. The flexible, stimuli-responsive structural transformation of the ICT complexes offer a new perspective for designing processable CT systems with controlled hierarchical self-assembly and electronic structures.


INTRODUCTION
Ionic CT (ICT) complexes have been receiving great interest from chemists, physicists, and materials scientists because of their attractive electronic properties. The first significant breakthrough in ICT complexes is the discovery of the first metallic conduction in tetrathiafulvalene/7,7,8,8-tetracyanoquinodimethane (TTF-TCNQ) (Ferraris et al., 1973). Its high electrical conductivity originates from the segregated alignment of the ionized donor (D) and acceptor (A) molecules (Kistenmacher et al., 1974). These findings have led to the development of related materials and applications (Frére and Skabara, 2005;Pauliukaite et al., 2007;Piek et al., 2018;Fujihara et al., 2020). On the other hand, another type of ICT complexes, i.e., those consist of alternately stacked arrays of the ionized D and A molecules, have recently been attracted attention because they are expected to serve as potential platforms for designing advanced materials such as organic ferroelectrics (Horiuchi and Tokura, 2008;Kobayashi et al., 2012;Takehara et al., 2019), multiferroics (Kagawa et al., 2010;Wang and Zhang, 2020), and photovoltaics (Nakamura et al., 2017). In contrast to the conventional neutral CT complexes, reports on ICT complexes have been largely limited to crystalline solids. Although room-temperature ferroelectricity has been reported for crystalline supramolecular ICT complexes (Tayi et al., 2012), they are currently regarded as neutral CT complexes and the suggested effect of crystal defects made the CT-ferroelectricity relationship indecisive (D'Avino et al., 2017;Tayi et al., 2017;Chen et al., 2019). Not limited to this issue, crystals, in general, are not suitable for applying ICT characteristics for developing useful devices that require the control of molecular orientations continuously from the molecular to macroscopic scales. It is also desirable that the ICT complexes show dynamic self-assembly and self-healing properties so that their physical properties are determined without the serious influence of crystalline defects. These problems will be solved by developing soft, self-assembling ICT complex systems. Although the CT interaction has been used to prepare columnar liquid crystals (Ringsdorf et al., 1989;Wang et al., 2009;Das and Ghosh, 2014;Bé et al., 2015) and other supramolecular nanostructures (Han et al., 2018;Adelizzi et al., 2019), their classes of CT are mostly neutral or undefined. To date, only two columnar liquid crystals have been reported as ICT complexes. However, they fall short of the critical requirements, that is, the 1:1 stoichiometry of DA pairs (Stepień et al., 2007) and the evidence for alternate DA stacking (Saeva et al., 1982;Stepień et al., 2007). The difficulty arises from the lack of rational methodologies to obtain the actual ICT state and to secure the regular, supramolecular alternating alignment of the ionized D and A molecules in soft molecular self-assemblies.
To develop ICT complexes that show self-assembly properties, we designed alternating supramolecular copolymerization of liquid donors and a benchmark acceptor TCNQ. To form ICT complexes with the 1:1 stoichiometry, it is essential that the donors have significantly strong electron-donating properties. In addition, the donors and acceptors are required to select only alternate supramolecular copolymerization into linear ICT complexes without segregation of each component. In order to achieve such an alternating molecular arrangement in soft molecular systems, where stabilization by the lattice force in 3D crystalline solids is not available, at least one component molecule is required to have an adaptive property so that the other component can be accommodated in between them by allowing the structural mismatch. In this work, we focused on engineering donor molecules because it is more facile than modifying acceptor molecules. To meet the above requirements, we adopted room-temperature liquefaction of πdonors by introducing proper substituents because such π-donor liquids are expected to show a limited degree of intermolecular interactions between identical molecules. This feature is also advantageous to solubilize the low-molecular-weight π-acceptors and achieve adaptive self-assembly, thereby leading to the ordered, alternating supramolecular copolymerization of ionized donors and acceptors. The room-temperature π-liquid became widely known for octyl methoxycinnamate, which has been utilized as an ultraviolet absorbing agent over several decades (Marti-Mestres et al., 2000;Scalia and Mezzena, 2010). It was popularized by the development of liquid chromophores containing carbazole (Hendrickx et al., 1999;Hirata et al., 2011), anthracene Duan et al., 2013), oligo (pphenylene vinylene) (Babu et al., 2012), azobenzene (Masutani et al., 2014), and so forth (Snaith et al., 2006;Kamino et al., 2012;Li et al., 2013;Takeda et al., 2018;Ghosh et al., 2019;Isoda et al., 2019;Lu and Nakanishi, 2019;Ogoshi et al., 2019;Morikawa et al., 2020;Bai et al., 2021). These π-liquids have been utilized as liquid semiconductors (Hendrickx et al., 1999;Snaith et al., 2006;Hirata et al., 2011;Kamino et al., 2012;Li et al., 2013), solvent-free luminescent liquids (Babu et al., 2012Lu and Nakanishi, 2019;Bai et al., 2021), stimuli-responsive liquid (Takeda et al., 2018;Isoda et al., 2019;Ogoshi et al., 2019), liquid electret (Ghosh et al., 2019), photon upconverters (Duan et al., 2013), and solar thermal fuels (Masutani et al., 2014;Morikawa et al., 2020). Although some π-conjugated organic liquids reported to date show electron-donating or accepting properties, they are categorized as weak donors or acceptors (Babu and Nakanishi, 2013;Lu and Nakanishi, 2019). The CT complexes are classified by the degree of CT (ρ CT ), where ρ CT = 0 for neutral TCNQ and ρ CT = 1 for complete charge transfer as found for K-TCNQ (Chappell et al., 1981). The vast majority of existing CT complexes reported to date fall into the class of neutral CT complexes with smaller ρ CT values (0 < ρ CT < 0.5), and only those having large ρ CT values (0.5 < ρ CT ≤ 1) are referred to as ICT complexes. The neutral to ionic transition of CT complexes has been induced by applying pressure (Torrance et al., 1981b;Takehara et al., 2019) or at a considerably lower temperature of 81 K for a tetrathiafluvalne-p-chloranil complex (Torrance et al., 1981a;Okamoto et al., 1991). These conditions severely limit the applicability of ICT complexes for device applications. There exist no reports on the strong donor or acceptor πliquids that can reduce the counterpart molecules to give ICT complexes under ambient conditions, and no general strategy has been developed to obtain ICT complexes without applying high pressure or low-temperature conditions. Meanwhile, we have previously reported that CT interactions among onedimensional cationic mixed-valence platinum complexes are significantly enhanced by the integration with regularly aligned anionic synthetic lipid molecules (Kimizuka, 2000). It is thus reasonable that the introduction of the suitable molecular design cultivated by self-assembly research to solid-state ICT complexes would provide a new perspective to design functional, soft ICT complexes.
Herein, we describe a rational self-assembly approach to obtain well-defined, alternately stacked liquid crystalline ICT complexes. π-Conjugated room-temperature liquids of dihydrophenazine (DHP) derivatives that show the highest electron-donating ability ever were developed. Moderately bulky branched alkyl substituents are linked to the DHP units via spacer alkyl units, which molecular design not only increases the solubility but also creates a flexible void in between the πdonor molecules, allowing adaptive accommodation of acceptors SCHEME 1 | Liquid-crystalline ionic CT complexes self-assembled from DHP derivatives and TCNQ.
in the condensed state. By simply mixing equimolar liquid-DHP and TCNQ in solution and casting at ambient temperature, alternating supramolecular copolymerization facilely occurs into ICT complexes in which ICT complexes are linearly aligned in the core of liquid crystals (Scheme 1). The self-assembly of liquid donor and crystalline acceptor gives rise to a new form of liquid crystalline ICT complexes, which feature has been demonstrated for the first time. These ICT liquid crystals displayed physical stimuli-responsive dynamic structural transformation, which characteristics affords us opportunities to control their molecular alignment hierarchically from the nano-to-macroscopic scales.

Preparation and Electronic State of ICT Complexes
As a donor chromophore, DHP was selected since the pair of 5,10-dihydro-5,10-dimethylphenazine [DHP(Me)] and TCNQ, a strong acceptor, has been reported to give a crystalline CT complex with a relatively large ρ CT value (ρ CT = 0.5 ± 0.1) (Meneghetti et al., 1985), which indicates that the complex is with intermediate ionicity. The DHP chromophore was liquefied according to the strategy to reduce cohesive interactions, i.e., by introducing branched alkyl groups (2-octyldodecyl and 2-ethylhexyl substituents) into 3,4,5trialkoxyphenyl periphery groups of the donor chromophore DHP  and DHP(2-6), respectively] (Scheme 1), since we expected that these fluid and bulky side chains would promote solubilization and provide an adaptive space that accommodates TCNQ molecules without segregation. The length of branched alkyl chains in DHP(8-12) and DHP(2-6) was changed in order to tune their intermolecular interactions and guest-accommodating properties.
As expected, these DHP derivatives were obtained as isotropic, pale yellow liquids at room temperature (RT) ( Figure 1A). The viscosity of the liquid was comparable to that of liquid paraffin. Interestingly, a significantly low first oxidation potential [E •x 1 = −0.23 V (vs. Fc/Fc + )] was observed in the cyclic voltammogram of DHP(2-6) (Supplementary Figure 1). It is lower than that of the reported π-donor liquids [e.g., (Snaith et al., 2006)] and that of the representative donor, TTF [E •x 1 = −0.10 V (vs. Fc/Fc + ) (Keniley et al., 2013)], providing an unequivocal basis that these DHP derivatives fall into the category of the strongest π-conjugated electron-donor liquid. Since E •x 1 is comparable to the first reduction potential for TCNQ [E red 1 = −0.25 V (vs. Fc/Fc + )] (Endo et al., 2014), the formation of ICT complexes is expected from the pair of DHP derivatives and TCNQ. To prepare CT complexes of DHP(8-12)-TCNQ and DHP(2-6)-TCNQ, equimolar toluene solutions of DHP derivatives and TCNQ ( Figure 1B) were mixed. Interestingly, upon casting these solutions on quartz substrates, deep blue films ( Figure 1C) were obtained at RT. The absorption spectra of these films show broad peaks at 1422 nm (0.872 eV) for DHP(8-12)-TCNQ and at 1467 nm (0.845 eV) for DHP(2-6)-TCNQ, respectively (Figure 2A). These peaks are reasonably assignable to the ICT absorption bands by reference to that reported for the DHP(Me)-TCNQ crystal (0.84-0.89 eV) (Fujita and Matsunaga, 1980;Soo et al., 1981). It is to note that additional peaks are observed around at 360 nm (3.44 eV) with a shoulder component around 430 nm (2.88 eV) and at 600 nm (2.07 eV), which are also reported for DHP(Me)-TCNQ (3.41 eV, 2.85 eV and 1.98 eV) (Fujita and Matsunaga, 1980). These peaks are assignable to the intramolecular electronic transitions for anion and cation radicals formed in the ICT complexes, as referenced to the previous reports on K-TCNQ (3.17-3.39 eV and 2.00 eV) (Torrance et al., 1980;Ikegami et al., 2007) and DHP(Me)-PF 6 (3.3 eV and 2.6 eV) (Ohkura et al., 2011). The ρ CT values of these CT complexes can be determined based on the linear correlation between the charge of TCNQ and the frequency of  its C≡N stretching vibration (ν C≡N ) (Chappell et al., 1981). In IR spectra (Figure 2B), the ν C≡N was observed at 2197 cm −1 for DHP(8-12)-TCNQ and 2195 cm −1 for DHP(2-6)-TCNQ, while a neutral TCNQ (ρ CT = 0) gave the peak at 2222 cm −1 . As K-TCNQ (ρ CT = 1) was reported to give a ν C≡N peak at 2183 cm −1 (Chappell et al., 1981), ρ CT values for DHP(8-12)-TCNQ and DHP(2-6)-TCNQ are determined as 0.64 and 0.69, respectively (see details in the Supplementary Material). These ρ CT values are sufficiently large to conclude their ICT characteristics.  Figure 1D). Very interestingly, although the cast film is highly viscous, these domains underwent fusion and alignment by applying mechanical shear force (rubbing treatment). As shown in Figure 1E, a "dark" state with very little birefringence was observed when the sample was rubbed along the direction of the polarizer axis P (P || R). On the other hand, when P is 45 • from the rubbing direction (R), a bright image was observed with an anisotropic texture oriented along with R ( Figure 1F). Similar results were also obtained for the cast film of DHP(2-6)-TCNQ (Supplementary Figures 2B,C). These observations clearly indicate that the ICT complexes are in the liquid crystalline phase, which is distinct from Frontiers in Chemistry | www.frontiersin.org the liquid and crystalline phase revealed by each donor and acceptor component, respectively. It is noteworthy that the inplane macroscopic orientation of these liquid crystalline ICT complexes is controllable by applying mechanical force.

Structural Evidence for the Alternate Stacking
In order to analyze molecular alignments in these liquid crystalline ICT complexes, X-ray diffraction (XRD) measurements were conducted for the as-cast films. Figure 3A shows the XRD patterns obtained for DHP(8-12)-TCNQ. Strong diffractions are observed in the small-angle region, which can be assigned as (110) and (200) reflections of columnar rectangular (Col r ) liquid crystalline phases (a = 63.3 Å, b = 41.5 Å, c = 6.72 Å). Detailed data and assignments are shown in Table 1. The broad halos around 10 and 20 • are ascribed to reflections from the liquid-like cluster of branched alkyl chains. Importantly, a distinct peak is observed at 13.16 • (6.72 Å), which is assignable to a (001) reflection as the spacing coincides with the two-fold distance of typical π-π stacking (3.2-3.4 Å). It indicates the presence of highly ordered, periodical alignment of DHP molecules in the alternately stacked columnar DHP-TCNQ complex structures. Such a reflection from two-fold periodicity has not been commonly observed (Tsukruk et al., 1993;Park et al., 2003;Bé et al., 2015). Although it has been observed for a few columnar liquid crystals of non-ionic CT complexes (Ringsdorf et al., 1989;Das and Ghosh, 2014), the present UV-VIS, IR spectroscopy, and XRD data indicate that the self-assembly of DHP(8-12) with TCNQ form liquid crystalline ICT complexes.
The structural regularity of ICT complexes in the Col r phase and the absence of phase-separated TCNQ is further supported by the absence of reflections assignable to segregated TCNQ crystals ( Figure 3C). Although reflections derived from the ππ stacking of chromophores in typical columnar liquid crystals appear around 23-27 • , they are also not observed in the present DHP(8-12)-TCNQ system. It confirms that the stacking of identical DHP(8-12) chromophores is interrupted by the TCNQ molecules located in between them. The small lattice constant c (6.72 Å) observed for the Col r liquid crystalline phase of DHP(8-12)-TCNQ suggests that the central aromatic chromophores are oriented almost parallel to the ab-plane, i.e., with nearly perpendicular orientation with respect to the column axes.
To get further insight into the structure of ICT complex, single-crystalline CT complex was obtained from a crystalline DHP derivative (DHP1), which has methoxy substituents instead of the branched alkyl groups, and TCNQ. The singlecrystal X-ray structural analysis of DHP1-TCNQ·2CH 3 CN (Supplementary Table 1) clearly shows that DHP1 and TCNQ stack alternately, as shown in Figure 4. In addition, the TCNQ molecule is not at the midpoint between two DHP1 molecules  Table 1. but located closer to either one of the two, which is the characteristic of polar ICT complexes (Supplementary Table 2). The crystalline DHP1-TCNQ·2CH 3 CN showed IR spectral characteristics similar to those observed in liquid crystalline ICT complexes. As shown in Supplementary Figure 4, the peaks at 2203 cm −1 and 2188 cm −1 are assignable to b 1u and a g modes of ν C≡N in the TCNQ molecule, respectively (Meneghetti et al., 1985). The b 1u mode, which is unclear in the liquid crystalline ICT complexes, is well-identified due to the high regularity in the single crystal. The ρ CT value for DHP1-TCNQ·2CH 3 CN calculated from a g modes is 0.87, which indicates that the compound is in the ICT state. These data support that the liquid crystalline DHP(2-6)-TCNQ and DHP(8-12)-TCNQ also form alternate stacking with the ICT state, whereas their intercolumn packing structures should be different from that of DHP1-TCNQ·2CH 3 CN crystal.

Packing Structure for Liquid Crystalline ICT Complexes
The molecular packing model of DHP(8-12)-TCNQ and DHP(2-6)-TCNQ can be determined by the above information from XRD patterns. As can be seen from the CPK model (Figures 5A-C), DHP(8-12) possesses an oval disks structure with its long axis oriented parallel to the a-axis (Figure 5D). The size of oval discs was roughly estimated by considering the motion of liquid-like alkyl chains and their entanglement with those of the neighboring molecules (Figures 5D,E). This packing model would fit the face-centered orthorhombic lattice if these liquid crystals possessed 3D long-range ordering. Since the number of formula units in the unit cell (Z) of this packing model is four, the density (ρ) of the CT complexes is calculated to be 0.94 g cm −3 ( Table 1). This ρ value is reasonable for organic liquid crystals, supporting the validity of the current supramolecular packing model. The two coexisting liquid crystalline phases in DHP(2-6)-TCNQ would be attributed to the presence of bimodal distribution in the molecular orientation of TCNQ as schematically depicted in Figure 5F. The length of lipophilic alkyl chains thus plays an important role in regulating the structural order of columnar ICT liquid crystals. x + 1, y, z. Figure 6 shows polarized UV-Vis-NIR spectra of a unidirectionally rubbed film of DHP(8-12)-TCNQ prepared on a quartz substrate, with varying the angle between the polarizer axis (P) and rubbing direction (R). Both the ICT absorption (at 1422 nm) and the intramolecular electronic transition bands (at 360, 430, and 600 nm) can be seen. Interestingly, these spectral intensities reached a maximum when P ⊥ R (Figure 6 inset). Therefore, the transition dipole moment for CT absorption [parallel to the column axis (c-axis)] and that for intramolecular absorptions [parallel to the long axis of TCNQ (mainly b-axis)] should be oriented perpendicular to R. In other words, the uniaxial orientation of a-axis is induced along with R (Supplementary Figure 5). This rubbing-induced change in molecular alignment is distinct from those observed for round-discoidal columnar liquid crystals (Yoshio et al., 2004;Yasuda et al., 2006), and is rather similar to the behavior of rod-like liquid crystals. The unique structural transformation characteristics would be due primarily to the oval-like molecular structure of DHP derivatives and ICT interactions in the supramolecular copolymers.

Changes in the Macroscopic Orientation by Rubbing Treatment
The shear-force-responsive structural transformation characteristics are also confirmed by changes in the XRD patterns of randomly rubbed films. As shown in Figure 7A, (110) and (200) reflections of Col r phase were fused to a single peak (2θ = 2.79 • ), and the other peak appeared at 5.58 • after the rubbing treatment in DHP(8-12)-TCNQ. Since the experimental diffraction spacing (d exp ) of these peaks are 31.6 and 15.8 Å, respectively, Miller indices of (100) and (200) were reasonably assigned to these peaks ( Table 2), suggesting  that the liquid crystalline phase was changed from Col r phase to a smectic-like mesophase. Such coexistence of columnar and smectic phases has rarely been reported (Nguyen et al., 1990). This mechanical shearing-induced structural change was also observed for the short-chained DHP(2-6)-TCNQ, which showed more distinct peaks assignable to (h00) reflections (1 ≤ h ≤ 4) with the remaining (001) reflection related to the alternate π-stacking after the rubbing treatment ( Figure 7B; Table 2). However, the stability of macroscopic alignment of the shear-induced smectic-like phase under the repeated rubbing treatment was inferior to that of DHP(8-12)-TCNQ (Supplementary Figures 2D-F, 3). Therefore, the alkyl-chain units assume a large role in determining the inter-column interactions that contribute to the enhanced thermal stability. Longer and more entangled alkyl moiety in DHP(8-12)-TCNQ should maintain the macroscopic alignment even after repeated rubbing treatment. Although the long-range ordering along with alternate DA stacking, which is related to the intensity of (001) reflection, seems to get weaker during the structure transformation process, the strong ICT absorption band was maintained without shifting, as shown in Figure 6. It indicates that the alternate DA stacking was retained in the short-range due to the large cohesive energy of ICT complexes. The control on in-plane macroscopic orientations has not been observed for the past ICT complexes while laser-heat-induced dichroism has been reported for neutral CT liquid crystals (Van Winkle et al., 2018). These results enhance the potential of ICT complexes as processable functional electronic materials.

CONCLUSION
The strong π-conjugated electron-donor liquids  and DHP(2-6)] were newly developed. Upon casting the mixed toluene solution of liquid DHP derivatives and TCNQ, alternating supramolecular copolymerization cooperatively occurred into well-defined, alternately stacked ICT complexes linearly aligned in the columnar liquid crystalline phase. The significance of the present work is three-fold. Firstly, the strong liquid donor molecules were developed by covalently accumulating branched alkyl chains to the dihydrophenazine chromophore. Secondly, the ICT liquid crystals are easily obtained simply by casting the equimolar solutions of liquid donors and TCNQ at room temperature. The formation of continuous, alternating supramolecular ICT states in the 1D columns and their organization in liquid crystalline assemblies occurred in the course of dynamic concentration changes (i.e., casting), would be explainable by the presence of cooperativity in the self-assembly process. The ICT interactions occur between the liquid donors and TCNQ molecules, which evolved the distinct Col r liquid crystalline phases with the first clear evidence for the alternate stacking. Thirdly, the columnar liquid crystalline phases of ICT complexes are transformed into the smectic-like mesophase by applying mechanical shear force. The stimuli-responsiveness and macroscopic control in the in-plane molecular alignment of ICT complexes have been achieved for the first time. The emergence of the ICT liquid crystalline phase from alternating supramolecular copolymerization of liquid donors and acceptors discussed in this work gives rise to a new phase-crossover approach (Ishiba et al., 2015), which would be widely applicable to various combinations of π-conjugated liquids and molecular solids. These molecular hybrids would new properties based on the nano-interface effects (Yamamoto et al., 2020), and provide a new platform for developing soft molecular devices with unique electronic characteristics.

MATERIALS AND METHODS
Essential experimental procedures are described below. Other details are shown in the Supplementary Material.

X-Ray Powder Diffraction Measurement
The cast film of CT complex was fabricated on Si(100) wafer. Xray powder diffraction (XRD) patterns were collected using an X-ray diffractometer, SmartLab (Rigaku), in the 2θ scan range of 2-50 • using Cu Kα (λ = 0.15406 nm) radiation operated at 30 mA and 40 kV at RT. Sampling and scan widths were 0.01 and 0.1 • /min, respectively.

Single-Crystal X-Ray Structural Analysis
A single crystal of DHP1-TCNQ·2CH 3 CN (size: 0.20 × 0.05 × 0.02 mm) was mounted on a glass tube with grease. Singlecrystal X-ray data were collected on a CCD diffractometer (Rigaku Saturn VariMax) with graphite-monochromated Mo Kα radiation (λ = 0.71075 Å). The temperature was set at 293 K by using a Japan Thermal Engineering temperature controller. Diffraction intensities were integrated by using CrystalClear software (Rigaku). The crystal structures were solved by using direct methods [SHELXS-97 (Sheldrick, 2008)], followed by Fourier syntheses. Structure refinement was performed by using full-matrix least-squares procedures using SHELXL (Sheldrick, 2015) on F 2 in the Yadokari-XG 2009 software (Wakita, 2001;Kabuto et al., 2009). Crystallographic Data for DHP1-TCNQ·2CH 3 CN CCDC-2056279 contains the supplementary crystallographic data for DHP1-TCNQ·2CH 3 CN. It can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.