Characterization of TpBpy and Re-TpBpy.
Re-TpBpy is constructed by long-range ordered 2D sheets through the layer to layer stacking as shown in Fig.1a with the synthesis process summarized in Fig. S1. The characterization of TpBpy and Re-TpBpy was achieved by powder X-ray diffraction (PXRD), X-ray photoelectron spectroscopy (XPS), and Fourier Transform Infrared (FT-IR). PXRD patterns of both TpBpy and Re-TpBpy match well with the simulated AA stacking structure in the hexagonal space group (P6). After Re-complex incorporation, the crystalline structure of TpBpy remains unchanged. The XPS spectra confirmed the anchoring of Re-complex to the host TpBpy only through its bipyridinic units24 (for detailed XRD and XPS characterization, see Fig. S2 and S3 in the supporting information). The FT-IR spectrum (Fig. 1b) of Re-TpBpy manifest the preserved chemical functionalities of pristine TpBpy while two additional peaks arising at 2025 cm−1 and 1887 cm−1 can be attributed to the C=O stretching vibration in the Re(CO)3Cl moiety23. Additionally, compared with the FT-IR spectrum of Re(CO)5Cl and TpBpy, the C=O stretching bonds and the broadened C–N peak in the Re-TpBpy are slightly red-shifted, indicating the coordination of Re(CO)3Cl to the bipyridinic N atoms in the TpBpy. Our FT-IR result also excludes the existence of residual Tp and Bpy in both as-synthesized TpBpy and Re-TpBpy.
Steady-state spectroscopic study
Steady-state absorption and PL spectra first clarified the ground state features of the Re-TpBpy hybrid and its individual units (Fig. 2a). The absorption spectra of the pure Tp and Bpy both showed a single distinct absorption band of Tp (350-400 nm) and Bpy (380 nm). The absorption spectrum of Re-Bpy is identical to Bpy except for a subtle blue shift (maxima absorption at 360 nm) owing to the metal-to-ligand charge transfer (MLCT) [d(Re)-π*(bpy)]36,37 On the contrary, the absorption spectrum of TpBpy exhibits dual absorption bands with a narrow bipyridine n−π* transition band (324 nm) as well as a broad band at 508 nm for delocalized π electrons38. The similar absorption spectra between Re-TpBpy and TpBpy suggest the high ligand stability (i.e. chromophore function) after functionalization24. The slight blue shift of the spectrum for Re-TpBpy should be due to the metal-to-ligand charge transfer (MLCT) [d(Re)-π*(bpy)].
Fig. 2a also shows the emission spectra of all samples excited at the band edge(530 nm, blue curve) and well above the band edge (400 nm, red curve). Tp and Bpy share the same emission band at 500 nm upon the 400 nm excitation with moderate Stokes shift. In contrast, the emission spectrum of the Re-Bpy (λem = 585 nm) is broad with large Stokes shift (Δλ=225 nm), which can be attributed to the existence of a triplet metal-to-ligand charge-transfer (3MLCT) states 39. When excited at 530 nm, the emission spectra of TpBpy and Re-TpBpy are identical with emission bands at 620 nm. This indicates similar emissive states from delocalized π electrons in the two samples. When excited at higher energy (400 nm), the emission spectra of TpBpy and Re-TpBpy exhibit dual emission bands (i.e., 427 nm and 531 nm for TpBy, 431 nm, and 562 nm for Re-TpBpy). The origins of such multi-emission bands in COFs can be complicated where one hypnosis is the radiative recombination in the single units of the COF.40 We can obtain the same conclusion in the following analysis of the excited states. In summary, the optical transitions of TpBpy and Re-TpBpy are distinct from the ones of their original building block units. We can further calculate the optical band gaps (Eg) of Tp, Bpy, Re-Bpy, TpBpy and Re-TpBpy from the Tauc plots of the absorption spectra (Fig. 2b) to be 3.14 eV, 2.79 eV, 2.90eV, 2.26 eV, and 2.17 eV, respectively. The characterization with XPS determines the valence band maximum (VBM) position of Tp, Bpy, Re-Bpy, TpBpyand Re-TpBpy to be 1.43 eV, 1.99 eV, 0.96 eV, 1.89 eV, and 0.99 eV corresponding to the Fermi level, respectively (Fig. 2c). Based on such values, we can determine the band energy alignment of the samples, as shown in Fig. 2d.
Excited state structures caculation
In order to obtain insight into the excited-state structure of the compounds, we used a triformylphloroglucinol (Tp) terminated bipyridine (Bpy) molecular fragment (Fig. 3) to represent the COF structure. The TD-DFT at the M06-L41–44 /def 2 TZVP45,46 level of theory has been employed to calculate the electronic structure and model the electronic transitions. Fig. 3 exhibits the calculated electronic excitation spectra of the TpBpy and Re-TpBpy (orange curves), which can resemble the experimental absorption spectra (red curves). The calculated spectrum of TpBpy mainly consists of two electronic excitation bands at 528 nm (S1) and 436 nm (S2), where high energy band S2 is equally contributed by the electronic transition (HOMO-3 → LUMO+1) and (HOMO → LUMO+2). The low energy band S1 is dominated by the electronic transition from HOMO to LUMO level as illustrated in Fig. 3a. The low energy optical transition only occurs at the Bpy moiety whereas the high energy transition involves the electron population at both Tp and Bpy in the COF moieties. The modeled spectrum of Re-TpBpy also shows two pronounced electronic excitation bands where the high energy band is contributed by two electronic transition S3 (HOMO → LUMO+2, 427 nm) and S2 (HOMO-4 → LUMO+1, 441 nm) (Fig. 3b). The low energy band consists of one electronic transition S1 (HOMO-2 → LUMO+1, 558 nm). Compared with TpBpy, the low energy electronic transition in Re-TpBpy involves the excitation of the electron from the orbital in both Tp and Bpy moieties. The detailed calculated orbitals for both samples have been summarized in the supporting information.
Time-resolved Photoluminescence
In the next step, we studied the photoluminescence (PL) dynamics of the samples. The steady-state PL spectra of TpBpy and Re-TpBpy are identical in terms of emission energy and spectral shapes (Fig. 4a). However, the relative PL quantum yield (extracted from absorption calibrated PL intensities) of Re-TpBpy is much lower. This should be attributed to the PL quenching by the integration of the Re-complex. The shorter PL lifetime of Re-TpBpy measured from time-correlated single-photon counting (TCSPC) verify the additional non-radiative process (Fig.4b). The exponential fitting can resolve two components with lifetimes of 1.1ns (91%), 19ns (9%) for TpBpy and 716ps (92%), 40ns (8%) for Re-TpBpy. However, the lifetime of the fast components (i.e. 1.1 ns for TpBpy and 716 ps for Re-TpBpy) are limited by the response function in the TCSPC measurement. Therefore streak camera technique was employed to explore the ultra-fast process. A similar faster PL decay of Re-TpBpy than TpBpy can be observed in Fig.4c. The PL decays can be fitted by tri-exponential functions. The two fast components can then be fitted as 106 ps (74%), 481 ps (24%) for TpBpy and 98 ps (66%), 340 ps (31%) for Re-TpBpy.
Femtosecond transient visible absorption spectroscopy.
The excited-state dynamics of the samples were explored by transient absorption (TA) spectroscopy. We first excited the samples close to their band edge at 530 nm. In this case, all the excited species should populate the lowest excited states instantly. The TA spectra of TpBpy exhibit one broad negative band (B1) from 450 to 595 nm attributed to the band-edge ground state bleach (GSB) together with two positive excited state absorption bands (ESA, A1 and A2) from 600 nm to 700 nm (Fig. 5a). According to the above DFT calculation in Fig. 3a, 530 nm excitation will only trigger the transition to the lowest excited state (i.e. HOMO to LUMO) in TpBpy. Hence, A1 and A2 here should not be attributed to different levels of the excited state. One possible explanation is the excited state transform from a normal exciton state (A2) to a polaron state (A1) where the excitons are self-trapped within the local structure of the COF29. Such polaron formation also complies with the significant stokes shift from the PL spectra, as shown in Fig. 2a.
For Re-TpBpy, only one B1 can be observed with the absence of long-lived ESA (Fig. 5b). This already indicates the charge transfer from the excited states. A more quantitative analysis was then implemented using singular value decomposition (SVD) fitting (Fig. 5a&b, lower panel). The TA dynamics of TpBpy can be decomposed into four decay-associated components (t1- t4). The first three components (t1- t3) shared the same negative GSB signal with the identical position (B1), denoting the population of the lowest excited state. The difference between the first component (t1 = 2 ps) with the second and third components (t2 = 70 ps and t3 = 4 ns) appears as the blue-shifted ESA band from A2 to A1 by about 50 nm. TA kinetics at the A1 (Fig. 5d, blue curve) and A2 (Fig. 5e, blue curve) reveal the concurrent rising of A1 and decay of A2. This indicates the transformation of the lowest excited state (e.g. polaron formation) within 2 ps corresponding to the transition of ESA from A2 to A1 in TA spectra. Components 2 and 3 exhibits the same spectral feature corresponding to the depopulation dynamics of the same lowest excited state. The slowest component 4 featured as broad negative band with a lifetime exceeding the TA time window. This can also be visualized in the TA kinetics in Fig. 5c-e. After functionalization by the Re-complex, the TA dynamics of Re-TpBpy can also be decomposed into four components (t1- t4) with lifetime of t1 = 990 fs, t2 = 13 ps, t3 = 262 ps accompany with one ultra-long component ((Fig. 5b). Component t1- t3 of Re-TpBpy resembles the GSB feature as TpBpy but with shorter lifetimes as evidenced by the comparison of B1 kinetics in Fig. 5c. Most importantly, ESA bands are completely absent in components t2 and t3. This suggests the ultrafast charge transfer from the lowest excited state. In addition, the longest component t4 also exhibits narrower GSB at the band edge position compared with GSB in component t4 of TpBpy.
In order to monitor the dynamics of hot carriers, high energy excitation has also been employed in both samples. Compared with TA spectra excited at 530 nm, here the TA spectra of both TpBpy and Re-TpBpy (Fig.6a&b) exhibit one additional negative band (B2) around 450 nm (Fig. 6) with the slight red-shifted B1 to 515 nm. Since B2 appears in both TpBpy and Re-TpBpy, the additional bleach band should be attributed to the population of high energy/hot levels in the COFs unit. SVD fitting indicates that the dynamics of TpBpy can be described by four main components. The fastest component t1 (2 ps) consists of B1, B2, and A1. Component t2 (34 ps) features the same B1 and B2 bands but the ESA is blue-shifted to A2. The component t3 (480 ps) lifetime shares almost the same spectral features of component 2 except for the absence of B2. A similar lifetime (481 ps) can also be extracted in the PL decay of TpBpy (Fig. 4c), manifesting the radiative recombination of the band-edge charge carriers. The component t4 only contains B1 but the contribution is negligible. The above SVD analysis indicates the long-lived B1 versus short-lived B2 as also evidenced by the extracted TA kinetics in Fig. 6c and d (blue curve).
On the other hand, both A1 and A2 appear instantaneously which is different from the ones observed for 530 nm excitation. TA spectra of Re-TpBpy can also be fitted with four main components (t1 = 2 ps, t2 = 24 ps, t3 = 340 ps and one ultra-long component). The features of component t1 resemble those of TpBpy with a similar lifetime of 2 ps. Compared with 530 nm excitation, B2 with 400 nm excitation are long-lived in both t1- t3 up to 340 ps. The prolonged B2 band in Re-TpBpy suggests that the long-lived high energy excited state population in contrast to TpBpy as further illustrated by the TA kinetics in Fig. 6d. Furthermore, A1 disappears in component t2 and reoccurs in t3. This is also reflected by the different A1 kinetics (Fig. 6e, red curve) compared with the B1 and B2 kinetics (Fig. 6c&d, red curve) especially at the timescale between 5 to 20 ps. The absence of A1 in component t2 can be induced by two possible scenarios: 1) there exist two pools of Re-TpBpy where electron transfer from TpBpy to ReI occurs in one pool and absent in the other. 2) the charge transfer of hot electrons from the COFs to ReI centers is followed by the back-transfer to the LUMO level. In the following, we will demonstrate the latter is more likely evidenced by time-resolved IR spectroscopy results, which probes the transient population of electrons at ReI centers. The lifetime t3 (340 ps) can be obtained from the TRPL decay in Fig. 4c, manifesting radiative recombination with hot carriers, which accounts for the high energy emission band in the steady-state PL spectrum (Fig. 2a). Identical to TpBpy, component 4 of Re-TpBpy comprises only B1 with negligible amplitude. In short, the additional B2 band and the wider ESA band when excited at 400 nm in components t1, t3 reflect the long-live hot excited level population. On the other hand, the absence of A1 in component t2 confirms the charge transfer of hot electrons to ReI centers within 2 ps.
Femtosecond transient infrared absorption spectroscopy
In order to further characterize the excited state dynamics at the two excitation wavelengths, we measured the time-resolved IR (TRIR) spectra of the samples. TRIR can probe photo-induced electronic transitions at low energy such as molecular vibrations or intraband free carriers47–51. No TRIR signal can be observed in TpBpy and Re-Bpy when excited at 530 nm (Fig.7a and Fig. 7b). However, the TRIR spectrum of Re-TpBpy exhibits pronounced differential dips at 1850 cm-1 and 2040 cm-1 (Fig. 7c), resembling the spectral feature of pure Re-Bpy excited at 400 nm (Fig.7f). Such differential dips are the fingerprint features of excited [ReI(bpy)(CO)3]* as the C-O stretching vibration is perturbed due to the formation of Re radical species52. The TRIR kinetics in Fig. 7d suggests that the ReI radical is formed within 0.6 ps (rising time of the kinetics) together with 2 decay lifetimes (15 ps and 2.3 ns). Such formation time of the ReI radical is consistent with t1 in TA components (0.99 ps) (Fig. 5b), confirming the sub-picosecond electron transfer from TpBpy to the ReI center after excitation. The 15 ps decay lifetime is identical to the component t3 in TA (Fig. 5b). When excited at 400 nm, the TRIR spectra of both TpBpy and Re-TpBpy are dominated by the featureless positive absorption (Fig. 7 e&g), which is widely accepted as the sign of free carrier generation in semiconductor materials47,53,54. This means that the hot excited states reflected by the B2 and the broad A1 band in TA should all be populated by free carriers when excited at 400 nm. Moreover, the TRIR spectrum in Re-TpBpy features additional differential dips of the ReI radical, indicating the COFs-Re electron transfer occurs. We can decompose the dynamics of ReI radical (orange curve, Fig. 7h) by subtracting the TA kinetics at such mixed region (2040 cm-1, red curve, Fig. 7h) by the kinetics at the region only showing positive absorption (1850 cm-1, blue curve, Fig. 7h). Here the intensity of TA kinetics at 1850 cm-1 is scaled up by the amplitude ratio between 1850 cm-1 and 2040 cm-1 as extracted in Fig. 7g (A2040 cm-1 /A1850 cm-1 = 1.9) with only free carrier contribution in COFs. The deferential kinetics (i.e. the orange curve in Fig. 7H) shows a 0.8 ps building up time followed by a 26 ps decay, which is consistent with the above argumentation that the hot electrons are injected to ReI center within the picosecond and rebounce to the S1 level of TpBpy in 26 ps. We also notice that such kinetics is different from the depopulation of photo-excited pure [ReI(bpy)(CO)3]* (green curve, Fig. 7h). This means the back transfer or geminate recombination of injected electrons in ReI center is faster than the electron-hole recombination in the ReI(bpy) moiety.