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A Local CC2 and TDA-DFT Double Hybrid Study on BODIPY/aza-BODIPY Dimers As Heavy Atom Free Triplet Photosensitizers for Photodynamic Therapy Applications Mohammad R. Momeni, and Alex Brown J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.6b02883 • Publication Date (Web): 01 Apr 2016 Downloaded from http://pubs.acs.org on April 4, 2016

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The Journal of Physical Chemistry

A Local CC2 and TDA-DFT Double Hybrid Study on BODIPY/aza-BODIPY Dimers As Heavy Atom Free Triplet Photosensitizers for Photodynamic Therapy Applications Mohammad R. Momeni and Alex Brown∗ Department of Chemistry, University of Alberta, Edmonton, Alberta, T6G 2G2 Canada E-mail: [email protected]

∗

To whom correspondence should be addressed

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Abstract A series of 11 different BODIPY dimers is carefully examined by means of ab initio and TDA-DFT methods. Vertical and 0–0 excitation energies along with the tetraradical character of these dimers are determined. Possible application of a series of linked dimers for photodynamic therapy (PDT) was investigated through computing their excitation energies, spin–orbit coupling matrix elements and singlet–triplet energy gaps. Finally through a systematic investigation of a series of 36 different BODIPY and aza-BODIPY dimers, a new class of near IR heavy atom free photosensitizers for PDT action is introduced.

Introduction Boron-dipyrromethenes (BODIPYs) are a very important class of organic fluorophores which have numerous applications such as laser dyes, 1,2 labelling and fluorescent indicators and probes, 3,4 imaging and sensing agents, 5,6 and compounds for electrochemistry and electrogenerated chemiluminescence. 7 They have also been shown to be efficient singlet oxygen generators 8 and photosensitizers (PSs) in photodynamic therapy (PDT) applications. 9,10 In PDT treatment, the PS is locally injected to the target area (cancer tissues) and a laser beam is delivered to the area through endoscopes and fiber optic catheters. After shining the light, carcinogenic singlet oxygen (1 O2 ) is generated from already present triplet oxygen (3 O2 ) molecules inside cancer tissues, by an energy transfer from the excited triplet photosensitizer (3 PS) to the 3 O2 . There are certain conditions for the PS to be used as a PDT drug including: (i) low dark toxicity, i.e., the PS should be only activated by light, (ii) low photo bleaching rate, (iii) a preferential uptake in target tissues, and (iv) large intersystem crossing (ISC) rate and as a result a large singlet oxygen generation quantum yield, (v) singlet–triplet gap (∆E [S0 –T1 ]) close to that of oxygen molecule for the energy transfer to be efficient (about 1 eV). 9,12 It has been shown that appropriate substitution of the BODIPY and aza-BODIPY molecules makes these molecules ideal candidates for PDT 2


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puting their excitation energies, singlet-triplet gaps and spin-orbit coupling matrix elements (SOCs). 22 Based on the comparison of the results with an experimentally tested PDT drug they suggested a number of these dyes for PDT applications. Very recently, through a detailed benchmark study we showed that time-dependent density functional theory (TD-DFT) methods systematically overestimate excitation energies of BODIPYs and aza-BODIPY monomers. In the search for the reason of this large error, we found that these systems suffer from significant amounts of double electron excitations which in principle single electron based methods such as TD-DFTs are not able to capture; 23 we were not the first to make this attribution, see discussion of the role of double excitations in BODIPYs in the recent review of Le Guennic and Jacquemin 24 and references therein. Through systematic increase of the level of excitation in a series of coupled cluster calculations and also by careful examination of the configuration interaction vectors obtained from multi-reference computations, we showed that one needs an appropriate treatment of electron correlation in both the ground and excited states to tackle them. Our comprehensive benchmark of ab initio methods showed that local coupled cluster with singles and approximate doubles (LCC2) method is a very good compromise between accuracy and efficiency and can provide excitation energies with mean absolute errors (Mean AE) of ∼ 0.1 eV. On the other hand, Jacquemin and his coworkers have shown that combining scaled opposite spin configuration interaction singles and perturbative doubles (SOS-CIS(D)) with the TDDFT polarizable continuum model (PCM) reduces the Mean AE to 0.197 eV. 25 In another study, they showed that use of the wave function based Bethe-Salpeter approach reduces the Mean AE to 0.18 eV for these systems. 26 To test the performance of TD-DFT and ab initio methods on BODIPY and aza-BODIPY dimers, a benchmark study is performed on a test set comprised of 11 different dimeric species; three of these species have been examined previously using computational approaches by other authors. 27,28 Special attention is paid to the double hybrid functionals (DH-DFs) in which a fraction of perturbative doubles correction (D) is added to them by definition

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that could account for some of the needed electron correlation in these compounds (See Eq. 2). Next, a series of theoretically designed BODIPY/aza-BODIPY dimers is constructed by connecting two monomer molecules through ethylene, benzyl, acetyl and azo bridges. Previous experimental studies have shown that linking two BODIPY monomers through different heteroatoms leads to vastly different photophysical properties (e.g., see Refs. 29– 31). The possible application of these dyes in PDT is also studied through computing their SOCs. Finally, based on our findings on different linked dimers, a series of 36 different azobridged BODIPY dimers, depending on the position of the linkage unit, was examined and some of them are introduced as PSs for PDT application.

Computational Methods Geometry optimizations were performed using density functional theory (DFT) with the meta hybrid M06-2X 32 functional and the cc-pVDZ 33,34 basis set in the gas phase. Previous benchmark studies on BODIPYs have shown that the solvent effect on geometry and excited state properties of these dyes is negligible. 22,23 Since the impact of basis set size is moderate for geometry optimizations with density functional theory methods, 35 cc-pVDZ is a suitable choice for the purpose of this work. “Tight” convergence criteria, i.e., maximum force = 1.5 × 10−5 a.u., RMS force = 1.0 × 10−5 a.u., max displacement = 6.0 × 10−5 , and RMS displacement = 4.0 × 10−5 were applied for all ground state (S0 ) and excited state (S1 and T1 ) optimizations. An “Ultrafine” grid, i.e., a pruned grid of 99 radial shells and 590 angular points per shell, was used for numerical integration as results utilizing the M06-2X functional are shown to be strongly grid dependent. 36,37 Harmonic vibrational frequencies were computed at the same level of theory for the ground and excited states in order to characterize the stationary points as true minima, representing equilibrium structures on the potential energy surfaces. Symmetry was utilized whenever possible to expedite calculations especially for multi-reference methods.

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15 different density functionals were used for computing vertical excitation energies of three different singlet excited states. Pure BLYP 38–40 and PBE 41,42 functionals as well as the revised form of the PBE functional (revPBE) 43 with no HF exchange along with their corresponding three parameter B3LYP 44 and one parameter PBE0 45 and revPBE0 45 hybrid functionals with 20% and 25% HF exchange, respectively, were utilized. From rangeseparated functionals, LC-BLYP 46 and CAM-B3LYP 47 functionals were chosen. The idea of mixing MP2 electron correlation with non-local BLYP in DFT and building double hybrid density functionals was first introduced by Truhlar and coworkers in 2003. 48 However, the first practical DH-DF was proposed three years later by Grimme which was a B88 two parameter functional with HF exchange of ax = 0.53 and MP2 correlation of ac = 0.27 mixed with LYP correlation named B2-PLYP (eq. 1). 49 GGA EXC = ax EHF + (1 − ac )EGGA + ac EMP2 x + (1 − ax )Ex c c

(1)

In excited state DH-DF, the excitation energy ω which is calculated from the singles based time dependent or Tamm-Dancoff approximated (TDA) DFT computations is added with a fraction (ac ) of double corrections (D) to the CIS method (eq. 2).

ωTD(A)−B2PLYP = ω + ac ∆(D)

(2)

Schwabe and Grimme reported the mPW2-PLYP 50 functional which was shown to yield good energetic results in the case of weak interactions. Since then many more DH-DFs are being added to this family based on different amounts of HF exchange (ax ), MP2 correlation (ac ) and the type of the GGA exchange correlation functional employed (eq. 1). Notably, Martin and co-workers 51 re-optimized the B2-PLYP functional for general purpose (B2GPPLYP), 51 kinetics (B2K-PLYP), 51 and thermochemistry (B2T-PLYP) 51 applications. Also Sancho-Garc´ıa and Pérez-Jiménez reported a DH-DF with ax = 0.602 and ac = 0.273 for π-conjugated systems (B2π-PLYP). 52 Several benchmark studies have proven the superiority 6


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of these DH-DFs over their hybrid, range separate hybrid and meta-hybrid ancestors. 36,53 Herein, we employ two different classes of DH-DFs based on the type of the GGA exchange correlation functional used; one group based on the BLYP functional, i.e., B2-PLYP, B2GPPLYP, B2π-PLYP, and mPW2-PLYP functionals, and another group based on the PBE exchange correlation, namely PBE0-2 54 and PBE0-DH, 55 developed by the Mao and Adamo groups, respectively. For all 15 DFT methods employed for excited state computations in this study, except the M06-2X functional, Resolution of Identity with chain of sphere algorithm (RIJCOSX) 56 was used for approximating Coulomb and exchange type integrals in the SCF cycles. This approach can expedite calculations up to two orders of magnitude without significantly losing accuracy when auxiliary basis sets are used. 57,58 The correlation fitting basis set, cc-pVDZ/C, developed by Hättig and co-workers was used for all the calculations, 59 unless noted otherwise. All the TD-DFT vertical excitation energies were obtained with Tamm-Dancoff and also frozen core approximations unless otherwise stated. Grimme and Neese have previously shown that excitation energies computed using the Tamm-Dancoff approximation are very similar to the full time-dependent calculations and in the cases of purely valence excitations and even difficult cases such as transition metals and large conjugated systems they are superior to the full TD results. 60 They also showed that their basis set dependences are very similar and inseparable. It has been shown by Goerigk and Grimme that DH-DF results are strongly basis set dependent and one should use a large basis set especially due to the MP2 perturbation part of the calculation. 36 Therefore the effect of enlarging the basis set from cc-pVXZ 33 to aug-cc-pVXZ (X = D and T) 34,61 on the excitation energy of compound (I) was investigated and the results are provided in Table 1. The effect of using density fitting basis sets, i.e., def2-TZVPP and def2-QZVPP, 62 was investigated and compared and contrasted to the former Dunning correlation consistent ones. As can be seen from Table 1, adding diffuse and polarization functions to the cc-pVDZ basis set to form aug-cc-pVTZ only lowers the S1 excitation energy by 0.079 eV. Going from the cc-pVDZ basis set to def2-QZVPP lowers the energy only by 0.074 eV. Overall, increasing

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Table 1: Computed B2-PLYP Vertical Excitation Energies (in eV) Using (AUG)-cc-pVXZ (X = D, T), def2-TZVPP and def2-QZVPP Basis Sets for Compound (I).(a) The Same Type of Auxiliary Basis Set Is Utilized for each Basis. Also Provided Are the Dominant Contributions Where H = HOMO and L = LUMO. Basis set

(a)

cc-pVDZ

S1 2.937 H → L (0.961)

S2 3.288 H-1 → L (0.838)

S3 3.626 H-3 → L (0.539) H → L+1 (0.351)

aug-cc-pVDZ

2.860 H → L (0.957)

3.228 H-1 → L (0.847)

3.553 H-3 → L (0.504) H → L+1 (0.384)

cc-pVTZ

2.884 H → L (0.959)

3.233 H-1 → L (0.846)

3.555 H-3 → L (0.522) H → L+1 (0.366)

aug-cc-pVTZ

2.858 H → L (0.957)

3.220 H-1 → L (0.849)

3.538 H-3 → L (0.500) H → L+1 (0.388)

def2-TZVPP

2.872 H → L (0.959)

3.227 H-1 → L (0.847)

3.548 H-3 → L (0.515) H → L+1 (0.373)

def2-QZVPP

2.862 H → L (0.958)

3.218 H-1 → L (0.848)

3.535 H-3 → L (0.506) H → L+1 (0.382)

The Experimental Value for the First Excited State of This Compound Is 2.868 eV. 63

the size of the basis set by adding more polarization and diffuse functions slightly lowers the excitation energy but has no major impact on the accuracy of our results. Hence, cc-pVDZ seems to be a suitable and cost efficient basis set and was utilized for our computations throughout this work unless otherwise stated. 0–0 transition energies were also determined using the M06-2X functional, recommended by Jacquemin et al. 64 The excitation energy was computed as E0−0 = Eadia + ∆EZP E where E adia is the energy difference between the optimized S1 and S0 states and the latter is the corresponding zero point energy difference of those two states. To predict the reliability of using a single-reference based method, the T1 diagnostic test

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of Lee and Taylor, which is based on the norm of the vector of single-excitation amplitudes from CCSD in a closed shell system, 65 was utilized. If the T1 value is smaller than 0.02, the system is considered to be dominated by a single-reference but if it is larger than 0.02, the system is considered to have (most likely) multi-reference character. According to this diagnostic test, no multi-reference character was found for the ground state of the studied species in the benchmark set (i.e., T1 < 0.02) (see Scheme 2). TD(A)-DFT results were compared and contrasted with electron correlated Laplace transformed density fitting local coupled-cluster singles and approximate doubles (LT-DFLCC2, abbreviated as LCC2 in the text), 66,67 Laplace transformed density fitting local algebraic diagrammatic construction second order (LT-DF-LADC(2), abbreviated as LADC(2) in the text), 68,69 and symmetry adapted cluster/configuration interaction (SAC–CI) 70 methods. The efficient direct algorithm was utilized for all the SAC–CI computations which corresponds to the conventional SAC–CI with NounlinkedSelection keywords (all other parameters were set to their defaults). Multi-reference complete active space self-consistent field (CASSCF) 71 and complete active space second-order perturbation (CASPT2) 72 computations were accomplished for all benchmark systems (except CASPT2 for X and XI, see Scheme 2). The CASPT2 computations utilized the internally contracted RS2C program. 72 The CASSCF wave functions were constructed by using equal weights of the S0 and S1 states. The CASPT2 computations used an IPEA shift, which is a correction to the zeroth order Hamiltonian, of 0.3. 73 According to the Fermi Golden rule, 74,75 the rate of non-radiative transition from any singlet excited state (Sn ) to any triplet excited state (Tm ) is expressed as

kISC =

2π ˆ SO |Tm i2 × FCWD hSn |H ~

(3)

ˆ SO |Tm i are the SOC integrals between pure spin states of Sn and Tn and FCWD where hSn | H is the Franck-Condon weighted density of states which is close to unity for a set of similar

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species. Determination of the ISC rate is extremely challenging for large molecules as it requires accurate assignment of different deactivation channels. 76 Instead chemists usually rely on semi-quantitative approaches for such investigations. 77 Therefore, SOCs are computed as a representative of ISC rates for these systems (see eq. 3). The SOCs were computed for three different excited singlet (Sn ) and triplet (Tm ) states using the T1 optimized geometry and the CAM-B3LYP/cc-pVDZ//UM06-2X/cc-pVDZ density functional. The spin-orbit mean-field (MNF-SO) quadratic response approach was used for SOCs calculations which utilizes an effective one-electron operator in which the two electron terms are evaluated as a sum over all α and β spin orientations; 78,79 For a comparison between different approaches for computing SOCs see Ref. 76 and references therein. Previous benchmark studies have demonstrated the accuracy and efficiency of this approach for transition metal complexes. 78 An error of less than 5% has been obtained for the one-electron MNF-SO method compared to the full Breit-Pauli (BP) SOC Hamiltonian approach (using CASSCF and MR-CI methods) in the case of light element (organic) compounds 80,81 which are subject of the current study. For DFT computations of SOCs using these two approaches see Ref. 22 and references therein. All the M06-2X ground and excited state geometry optimizations along with the SACCI computations were performed using the Gaussian 09 package. 82 LCC2, LADC(2), and CASSCF and CASPT2 computations were accomplished using the 2010 and 2012 versions of MOLPRO. 83,84 All the TDA-DFT computations were accomplished using the ORCA 3.0.2 package. 85 All the SOC calculations were performed using the DALTON 2015.0 code. 86,87

Results and Discussion For benchmarking purposes, a set of 11 different BODIPY/aza-BODIPY based dimers is considered where the corresponding experimental data are available (Scheme 2 and Table 2; for the optimized geometries and Cartesian coordinates see Figure S2 and Table S1,

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respectively, SI).

Scheme 2: Structures of the Benchmark Set Considered in This Study. Iso-electronic five and six membered fused bis BODIPYs (I and II) as well as BODIPY dimers (III–V and VII–IX and aza-BODIPY, VI) in which BODIPY monomers are attached in different positions are considered in the test set. Benzene fused near IR (NIR) light emitting BODIPY dimers (X and XI) were also included as these types of chromophores are well known to be challenging due to their low highest occupied (HOMO) and lowest unoccupied (LUMO) molecular orbital gap. Compounds I and II are both isomers and isoelectronic, IV and V as well as X and XI are syn and anti isomers, VI is the aza-substituted isomer of IV and III–V. Also, VII–IX are isomers which are different in the position of connection. As is shown in the next section, these structurally similar BODIPY dimers illustrate very different photophysical properties that could be challenging for benchmarking purposes. Compound VII has been the subject of recent TD-DFT, CC2, and ADC(2) computations to examine the role of excitonic coupling on the absorption spectrum (these effects are ne11



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glected in the present work) and to understand the nature of the emissive state. 27 Chibani et al. 28 have determined the excitation energies (i.e., the energies of the absorption/fluorescence crossing point) of compounds X and XI based on TD-DFT results wth several functionals (B3LYP, PBE0, BMK, M06-2X, CAM-B3LYP, and ωB97X-D).

Benchmark of Ab initio and TDA-DFT Excitation Energies Two different pure DFT functionals, Perdew, Burke and Ernzerhof (PBE and revPBE) and Becke exchange and Lee, Yang and Parr correlation functional (BLYP), and their hybrid (PBE0, revPBE0 and B3LYP) and range separated hybrid (RSH: LC-BLYP and CAMB3LYP) functionals along with their double hybrid counterparts (B2-PLYP, B2GP-PLYP, B2π-PLYP, mPW2-PLYP, PBE0-2 and PBE0-DH) were chosen for computing vertical excitation energies of all the chromophores considered in the test set (Scheme 2 and Table 2). Mean deviation (MD), mean absolute deviation (MAD), maximum-minimum deviation difference (Max-Min) root-mean-square deviation (RMSD), and variance (σ) of all methods are presented in Table 2. In close agreement with our previous findings on BODIPY monomers, 23 the smallest MAD is found for the pure functionals and the highest for the RSH functionals (Table 2). The hybrid B3LYP functional is slightly better than PBE0 (∆MAD = 0.069 eV); however, their pure versions are almost identical from accuracy viewpoints. Also, the revised forms of the PBE functional give similar results to their PBE ancestors. The RSH LC-BLYP and CAM-B3LYP functionals with MADs of 0.823 eV and 0.772 eV provide the poorest results. Inclusion of geometric relaxation of the ground and excited electronic states of BODIPY dimers in the 0–0 M06-2X computations (M06–2X(0−0) ) removes some of the errors in the vertical approximation approach and decreases the MAD from 0.563 eV to 0.235 eV and RMSD from 0.626 eV to 0.302 eV (Table 2). For compounds X and XI, where comparison can be made to the absorption/fluorescence crossing point energies of Chibani et al. 28 determined using full TD with B3LYP, CAM-B3LYP, PBE0, and M06-2X functionals, one finds the present TDA vertical excitation energies to be larger by ca. 0.0-0.8 eV depend12


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ing on functional; these difference arise both from the TDA and vertical excitation energy approximations. Comparing B2LYP (a hybrid functional without (D) correction) with its DH version (i.e., B2-PLYP with 0.27 fraction of (D) correction) clearly illustrates the impact of electron correlation from a wave function based method to a TD-DFT functional as the MAD drops by more than a factor of two (from 0.436 eV to 0.213 eV) (Table 2). The MAD further drops to 0.188 eV in the B2GP-PLYP DH-DF but slightly increases in the cases of B2π-PLYP and mPW2-PLYP (0.249 and 0.246 eV, respectively). Going from hybrid PBE0 to PBE0-DH, the MAD decreases only by 0.081 eV but it significantly drops by 0.300 eV for the PBE0-2 method. Therefore, it seems that a balance between the amount of HF exact exchange and MP2 correlation is more important in the case of the PBE based DH-DFs than BLYP based ones. Overall, B2GP-PLYP and PBE0-2 DH-DFs provide the lowest MADs among all 15 different TD(A)-DFT methods studied herein; B2GP-PLYP also provides the lowest variance. Therefore, B2GP-PLYP is highly recommended for these systems if one bases results solely on vertical excitation energies rather than on more sophisticated, and computationally expensive, approaches requiring excited state optimization. In two separate studies, Moore and Autschbach 96 and Ziegler and coworkers 97 have benchmarked excitation energies of linear cyanine dyes with the full TD and with the TDA approximation. Both groups found that the TDA approximation tends to overestimate the calculated singlet excitation energies by up to 0.2 eV and underestimate the triplet excitation energies of these dyes leading to exaggerated singlet–triplet gaps. 97 Herein, we investigated the effect of using the TDA approximation for two pure exchange-correlation functionals, i.e., BLYP and PBE density functionals. As can be seen from Table 2, neglecting the so-called B matrix in the TDA approximation leads to overestimation of the results for all of the considered species except compounds (III) and (X). Considering the statistical data, and in close agreement with the work of Moore and Autschbach, 96 the TDA calculations for these two functionals overestimates the energies with respect to the TD values (MD, excluding compounds III and X, for TD versus TDA is 0.08 eV). On the other hand, the MAD with respect to experiment

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Table 2: Computed Vertical Excitation Energies (in eV) Using 16 Different TDA-DFT Functionals and Five different Ab initio Methods and the cc-pVDZ Basis Set in the Gas Phase. Experimental Values (Exp.) Along with the M062X 0–0 and Vertical (M06–2X(0−0) and M06–2X(vert) , Respectively) Excitation Energies Are Tabulated for Comparison. Statistical Data (MD, MAD, Max– Min, RMSD, and σ) Are Also Shown for Each Method. Full TD Approach Is Compared to the TDA Approximation for the Cases of the Pure BLYP And PBE Functionals.(a) Method (b) Exp. BLYP BLYP (Full TD) B3LYP LC-BLYP CAM-B3LYP B2LYP B2-PLYP B2GP-PLYP B2π-PLYP mPW2-PLYP

I II III IV 2.868 2.638 2.214 2.357 3.170 2.922 2.058 2.038 2.977 2.828 2.068 1.931 3.490 3.488 2.592 2.421 3.773 4.155 2.999 2.826 3.740 4.041 2.989 2.773 3.407 3.503 2.772 2.437 2.937 2.702 2.508 2.070 2.958 2.800 2.566 2.127 3.104 3.019 2.630 2.218 3.053 2.909 2.584 2.168

PBE PBE (Full TD) revPBE PBE0 revPBE0 PBE0-DH PBE0-2

3.185 2.924 2.068 2.052 1.995 1.786 2.165 1.533 2.022 2.988 2.830 2.077 1.945 1.938 1.729 2.114 1.524 1.988 3.190 2.933 2.072 2.055 2.000 1.788 2.167 1.540 2.028 3.566 3.621 2.703 2.513 2.572 2.266 2.574 2.294 2.524 3.569 3.629 2.705 2.516 2.575 2.269 2.574 2.300 2.528 3.399 3.462 2.759 2.431 2.540 2.217 2.420 2.445 2.636 2.967 2.900 2.574 2.157 2.280 2.066 2.187 2.561 2.426

M06–2X(vert) M06–2X(0−0) SAC–CI LCC2 LADC(2) CASSCF CASPT2 (a)

V 2.036 1.981 1.938 2.459 2.916 2.884 2.551 2.173 2.247 2.335 2.277

VI 1.781 1.777 1.718 2.186 2.556 2.513 2.226 1.924 2.004 2.064 2.010

3.534 3.912 2.774 2.566 2.671 2.286 3.162 2.872 2.356 2.348 2.444 2.076 2.769 3.034 2.078 1.817 1.964 1.625 3.006 3.150 2.394 1.972 2.104 1.795 2.982 3.121 2.370 1.939 2.061 1.742 3.755 5.013 3.477 2.776 2.918 2.615 2.881 2.915 2.080 1.910 1.972 1.721

VII 2.194 2.153 2.105 2.538 2.616 2.618 2.416 2.184 2.192 2.264 2.240

2.408 2.232 1.605 1.867 1.861 2.392 1.924

VIII 2.450 1.522 1.514 2.130 3.188 3.148 2.510 1.874 2.546 2.454 2.079

IX X XI MD 2.407 1.792 1.636 – 2.015 1.922 1.984 –0.076 1.982 2.080 1.857 –0.125 2.422 2.434 2.332 0.374 3.149 2.685 2.564 0.823 2.980 2.689 2.525 0.772 2.669 2.432 2.248 0.436 2.299 2.128 1.951 0.034 2.372 2.126 1.967 0.139 2.465 2.224 2.055 0.224 2.400 2.202 2.024 0.143 1.934 1.998 2.090 1.867 1.939 2.001 2.569 2.386 2.573 2.387 2.435 2.246 2.099 1.965

2.924 2.784 2.468 2.433 2.480 2.344 2.070 2.106 1.704 2.398 2.296 1.897 2.380 2.279 1.894 2.891 3.357 3.072 – – – (b)

Graphs of the Statistical Data Are Provided in Figure S16, SI. from Refs. 20,63,88–95

14

2.299 2.162 1.595 1.828 1.786 2.934 –

MAD – 0.269 0.272 0.433 0.823 0.772 0.436 0.213 0.188 0.249 0.246

Max-Min – 0.924 0.873 0.786 1.095 0.957 0.805 0.566 0.350 0.428 0.403

RMSD – 0.364 0.364 0.497 0.867 0.813 0.498 0.265 0.221 0.291 0.278

σ – 0.356 0.342 0.327 0.272 0.259 0.240 0.263 0.172 0.187 0.238

–0.065 –0.117 0.060 0.474 0.477 0.420 0.164

0.267 0.270 0.267 0.502 0.505 0.421 0.202

0.912 0.874 0.903 0.866 0.870 0.819 0.353

0.362 0.361 0.361 0.571 0.574 0.486 0.234

0.356 0.342 0.356 0.318 0.319 0.245 0.245

0.563 0.231 –0.182 0.030 –0.004 0.984 –0.062

0.563 0.235 0.254 0.189 0.183 0.984 0.118

1.065 0.543 0.548 0.498 0.458 2.177 0.434

0.626 0.302 0.316 0.240 0.236 1.133 0.185

0.276 0.195 0.258 0.239 0.236 0.562 0.213

Experimental (Exp.) Data Are Taken


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remains essentially unchanged between the TD and TDA results for the BLYP and PBE functionals. For compound VII, the TDA-B3LYP/cc-pVDZ value of 2.538 eV is 0.26 eV larger than the TD-B3LYP/cc-pVDZ value of 2.28 eV computed by Knippenberg et al. 27 Overall, in contrast to the linear cynanine dyes, and based upon the limited pure functionals tested here, TDA is a more benign approximation for the BODIPY dimers considered in the test set. Five different ab initio methods were tested for these molecules and the excitation energies and statistical evaluations are depicted in Table 2 along with the TDA-DFT and 0–0 results. Expectedly, the CASSCF method significantly overestimates the excitation energies and yields the highest MAD and RMSD of 0.984 and 1.133 eV among all the studied methods most likely due to lack of dynamic electron correlation (For details of active spaces of all species see Figures S3-S14, SI). On the other hand, the CASPT2 method provides the best estimate to the experiment with MAD = 0.118 eV and RMSD = 0.185 eV. Local CC2 and ADC(2) methods with MADs of 0.189 and 0.183 eV are closest to the CASPT2 method. SAC-CI with MAD = 0.254 eV and RMSD = 0.316 eV is poorer than both best estimates of DH-DFs (i.e., B2GP-PLYP and PBE0-2) and ab initio (LCC2 and LADC(2)) methods. Overall, based on our statistical analyses and for the sake of consistency with our previous study, 23 the LCC2 method seems to be a good compromise between accuracy and efficiency. Therefore, LCC2 is employed hereafter unless otherwise stated (For the graphs of statistical analyses of all methods see Figure S16, SI).

Linkage Control Over Excitation Energies and Intersystem Crossing As stated in the original paper, 20 BODIPY dimers attached in the [1,1] and [1,4] positions (molecules VIII and IX, Scheme 3) possess singlet oxygen generation abilities due to the orthogonal arrangement of the monomers (For the effect of methyl substitution on the vertical excitation energies of these species see Table S2, SI). This orthogonality results in a tetraradical electronic configuration in which four electrons are distributed between four molecular 15



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orbitals (HOMO-1, HOMO, LUMO, and LUMO+1) which ultimately leads to ISC rate enhancement. 21 However, as mentioned in the Introduction section, these BODIPY dimers absorb light outside the therapeutic window (650 ∼ 900 nm) and therefore are not applicable for PDT applications. 20 In search for heavy atom free NIR BODIPY dimer based PSs, two BODIPY monomers were connected through an auxiliary group: ethylene, azo, acetylene, and phenyl moieties (Scheme 3). CASSCF occupancies, for the two highest occupied (HOMO and HOMO-1) and two lowest unoccupied (LUMO and LUMO+1) molecular orbitals (MOs) were computed for all species (Table 3, for the MOs of all species see Figures S3-S15, SI). The same active space was used for all species to ensure the equal footing of our computations. SOCs for the X, Y, and Z components were computed using the M06-2X T1 optimized geometries and vertical LCC2 excitation energies using their corresponding ground state S0 geometries. The singlettriplet energy gap between the ground singlet and first excited triplet state (∆E [S0 –T1 ]) was computed for all species using the M06-2X and LCC2 methods and the gap between the first-excited singlet state and nearest triplet (∆E [S1 –Tn ]) was determined with LCC2 (see Table 3). For a comparison between the LCC2 and M06-2X computed S1 –S3 and T1 – T3 vertical excitation energies of all species see Table S3, SI. The results are compared and contrasted to the BODIPY monomer itself as well as to the chlorin molecule as the truncated model of the meta-tetrahydroxyphenyl chlorin (m-THPC) as a commercially available PDT agent. We note that our computed SOC value of –0.5 cm−1 for the chlorin molecule at the CAM-B3LYP/cc-pVDZ level is close to the reported value of +0.3 cm−1 for the m-THPC molecule at the B3LYP/6-31+G(d) level of theory. 22 All the studied linked dimers show tetra-radical character in which dimer VIII N possess the highest and IX N the lowest amount among all (Table 3). The computed LCC2 excitation energies for the S1 state shows that the excitation energy for the former molecule is 0.044 eV higher than the unsubstituted dimer (VIII) whereas the latter with excitation energy of 1.720 eV shows a significant red shift of 0.568 eV and is closest to that of the chlorin

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! Scheme 3: Linked BODIPY Dimers Considered in This Study. molecule. The excitation energies for all the other species fall close to or above the directly linked molecules (i.e., VIII and IX). The largest computed SOC belongs to the VIII Ph species with 9.27 cm−1 for its component compared to –1.35 cm−1 for the component of the reference molecule (VIII). The azo-linked dimers (VIII N and IX N) possess large SOCs compared to their reference species (–4.04 and 0.57 cm−1 , respectively). Overall, except dimer IX and IX Ph the rest of the studied species have SOCs larger than the chlorin molecule whereas the BODIPY monomer itself shows SOC values of zero (Table 3). As mentioned in the introduction, the singlet-triplet gap of the photosensitizer needs to be equal or greater than the energy required for exciting the 3 O2 molecule to its excited singlet state. As can be seen from Table 3, all the studied BODIPY dimers possess gaps higher than 1 eV with the smallest gap belonging to the IX N molecule and the largest to the IX Ph compound. For comparison, the singlet-triplet gap for the chlorin molecule is computed to be 1.409 eV at the same level. Also, the energy differences between different deactivation

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Table 3: Computed CASSCF Occupancies, LCC2 Excitation Energies (in eV), SOCs (in cm−1 ), And 0–0 and Vertical Singlet-Triplet Gaps (in eV) of the Studied BODIPY Dimers Using the cc-pVDZ Basis Set in the Gas Phase. Species VIII VIII CH VIII N VIII C VIII Ph

CASSCF Occupancies ∆E [S0 -S1 ] HOMO-1 HOMO LUMO LUMO+1 LCC2 (eV) 1.71 1.29 0.64 0.36 2.388 1.65 1.30 0.68 0.38 2.193 1.27 1.02 1.00 0.71 2.432 1.64 1.29 0.69 0.38 2.344 1.61 1.29 0.71 0.39 2.276

ˆ SO |Tn i (cm−1 ) hS1 |H ∆(E+ZPE ) [S0 -T1 ] Involved States X Y Z M06-2X (eV) S1 →T2 0.47 –0.44 –1.35 1.691 S1 →T1 0.04 –0.19 –0.68 1.649 S1 →T2 –1.19 –4.04 0.00 1.707 S1 →T2 –0.15 0.00 –0.61 1.686 S1 →T2 3.14 4.94 9.27 1.642

∆E [S1 -Tn ] LCC2 (eV) –0.687 –0.564 –0.552 –0.626 –0.540

IX IX CH IX N IX C IX Ph

1.54 1.79 1.84 1.61 1.46

1.35 1.44 1.38 1.60 1.43

0.67 0.58 0.65 0.40 0.59

0.44 0.19 0.13 0.38 0.51

2.288 2.285 1.720 2.420 2.509

S1 →T2 S1 →T1 S1 →T2 S1 →T1 S1 →T2

–0.16 0.83 0.00 –0.02 –0.07

0.29 –2.69 0.00 –1.47 –0.07

0.00 0.00 0.57 0.00 0.00

1.637 1.621 1.089 1.579 2.381

–0.708 –0.749 –0.553 –0.912 0.354

BODIPY Chlorin

1.87 1.90

1.36 1.36

0.73 0.64

0.08 0.11

2.650 1.749

S1 →T1 S1 →T1

0.00 0.03

0.00 –0.50

0.00 –0.05

1.674 1.409

–0.902 –0.279

channels are computed using the LCC2 method and shown in Table 3. The [S1 –Tn ] gaps of the two azo-substituted dimers (VIII N, IX N) are almost the same and are comparable to their corresponding reference species and are also closest to the chlorin molecule (–0.274 eV difference) among all. Except XI Ph and XI C the [S1 –Tn ] gaps for the rest of molecules fall close to each other and stay ∼ 0.5 eV below that of the chlorin molecule.

Azo-substituted BODIPY/aza-BODIPY Dimers It was found in the previous section that substituting two BODIPY monomers through an azo linkage in compound IX N shifts the absorption value of the directly linked BODIPY dimer up to ∼ 130 nm towards the red region which is beneficial for PDT purposes. To further investigate the effect of azo substitution on the excited state properties of the BODIPY as well aza-BODIPY dimers, a series of 36 different (aza-)BODIPY based dimers, depending on the position of the connection of two monomers, was systematically investigated. Vertical excitation energies of three different singlet excited states (S1 –S3 ) were computed using the LCC2 method and the cc-pVDZ basis set in the gas phase (see Table S4 and Figure S17, SI for the excitation values and their corresponding assignments). Position of connection of two monomers has a remarkable impact on the excitation en-

18


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ergies of the formed dimers. The trend of excitation energies to S1 for BODIPY substituted dimers is as follows: Bo[3,3] > Bo[3,1] > Bo[4,1] > Bo[1,1] > Bo[5,1] > Bo[4,3] > Bo[5,3] > Bo[4,4]-Anti > Bo[4,4]-Syn > Bo[5,4] > Bo[5,5] (Table S4, SI). Similar to the BODIPY dimers, the Az[3,3] dimer possesses the largest excitation energy and Az[5,4] and Az[5,5] the smallest ones. Overall, absorptions in the aza-BODIPY dimers are red shifted compared to their BODIPY dimer analogues; the maximum red shift of 1.132 eV corresponds to the [3,3] position and the minimum of 0.177 eV to the [4,4]-Syn position (Table S4, SI). Linking BODIPY and aza-BODIPY dimers with an N2 group leads to a new class of azo-substituted BODIPY (Bo[n,n]-N2 , n = 1–5) and aza-BODIPY (Az[n,n]-N2 , n = 3–5) dimers. In all 18 different azo-substituted structures studied in this work, the S1 excited state corresponds to a transition from HOMO → LUMO which is related to an nN → π* transition. In general, N2 substitution shifts the absorption energies of all the BODIPY and aza-BODIPY dimers more to the red region; except in compounds Bo[4,4]-Syn, Az[4,3] and Az[5,4]. The SOCs were computed for all species possessing excitation energies lower than 2 eV or wavelengths longer than 620 nm (i.e., close to the therapeutic window) and the selected results are provided in Table 4. Except Az[5,3] and Bo[5,1]-N2 molecules with [S0 –T1 ] gaps of 0.637 and 0.915 eV, respectively, the rest of the dimers shown in Table 4 possess gaps higher than 1 eV required for exciting the oxygen molecule.The lowest [S1 –Tn ] gap corresponds to the Bod[4,4]-Syn molecule and the highest to the Az[5,3] molecule. The [S1 –Tn ] gaps of the rest are close to each other and around 0.6–0.7 eV. All the species grouped in Table 4 show significant SOCs compared to their corresponding directly linked and experimentally verified molecules. As mentioned before, the orthogonal arrangement of the BODIPY monomers in VIII and IX was responsible for their tetra-radical behavior and ultimately their applicability in PDT. Similarly, the linked Az[4,4]-N2 -Anti and Bo[5,4]-N2 dimers with non-planar geometries possess the highest SOC values (125.01 cm−1 for the component of the Az[4,4]-N2 Anti dimer and –8.97 cm−1 for the component of the Bo[5,4]-N2 molecule, see Figure

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Table 4: Computed Photophysical Properties of Selected Linked Dimers Using the cc-pVDZ Basis Set.

Species Bo[4,4]-Syn Bo[5,1]-N2 Bo[5,4]-N2 Az[4,3] Az[4,4]-Syn Az[4,4]-N2 -Syn Az[4,4]-N2 -Anti Az[5,3] (a)

∆E [S0 -S1 ] LCC2 (eV) 1.972 1.861 1.947 1.838 1.795 1.942 1.843 1.804

ˆ SO |Tn i (cm−1 ) hS1 |H X Y Z 0.00 0.00 –5.15 –4.80 0.13 0.81 –8.97 –0.55 1.65 0.02 0.00 5.80 4.19 0.00 0.00 0.09 0.04 –5.22 –29.96 125.01 0.00 0.00 0.00 –2.99 (a)

∆(E+ZPE ) [S0 -T1 ] M06-2X (eV) 1.785 0.915 1.141 1.139 1.317 1.157 1.210 0.637

(a)

∆E [S1 -Tn ] LCC2 (eV) –0.493 –0.647 –0.582 –0.721 –0.692 –0.754 –0.621 –0.885

All Excitations Correspond to S1 → T1 Except for Az[4,4]-N2 -Anti with a S1 → T2 Transition.

S17, SI for the optimized geometries). Hence, considering the computed vertical excitation energies, [S0 –T1 ] and [S1 –Tn ] gaps and SOCs, compounds Az[4,3], and Az[4,4]-Syn, and Az[4,4]-N2 -Anti with excitation energies of 1.838 eV (675 nm) 1.795 eV (691 nm), and 1.843 eV (673 nm), respectively, look promising candidates for PDT action. Our results are in close agreement with previous experimental findings that substituting BODIPY and aza20


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BODIPY monomers in the C–4 position is crucial for having a large ISC rate and therefore a good triplet PS. 11–15

Concluding remarks An extensive benchmark study on vertical excitation energies of 11 different BODIPY and aza-BODIPY dimers was performed using 15 different TDA-DFT functionals. 0–0 excitation energies were also obtained for all structures using the M06-2X meta hybrid functional. Among all the TDA-DFT functionals used, B2GP-PLYP and PBE0-2 double hybrid density functionals were found to yield the least amounts of mean absolute deviations (0.188 and 0.202 eV, respectively). Also, from the different ab initio methods tested in this work, the local coupled cluster method with singles and approximate doubles along with local algebraic diagrammatic construction second order yielded the best results and were closest to the CASPT2 method. In the search for near IR heavy atom free triplet photosensitizers based on BODIPY dimers, two of the previously proposed dimers for PDT action were further modified using different auxiliary groups (ethylene, acetylene, azo and phenyl moieties). The SOCs and CASSCF occupancies were computed for all species along with the LCC2 vertical excitation energies and [S1 –Tn ] singlet-triplet gaps. Finally, a systematic study on all possible azo-linked BODIPY and aza-BODIPY dimers was performed and triplet photosensitizers based on these molecules were introduced. Supplementary Information Selected geometrical parameters of all BODIPY dimers studied in the test set (Table S1). Effect of methylation on the vertical excitation energies of the orthogonal dimers (Table S2). LCC2 and M06-2X vertical excitation energies of the linked dimers (Table S3). LCC2 vertical excitation energies of all the azo-bridged dimers (Tables S4 and S5). M06-2X Cartesian coordinates of the S0 (Table S6), S1 (Table S7) and T1 optimized structures (Table S8). Numberings of BODIPYs/aza-BODIPYs (Figure S1). M06-2X S0 optimized structures (Figure S2). CASSCF optimized MOs of the BODIPY

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dimers (Figure S3–S14). M06-2X optimized MOs of all the linked dimers compared to Bidipy, chlorin and m-THPC (Figure S15). Plot of summary statistical analyses of the computed vertical excitation energies (in eV) of all the studied methods for the benchmark set (Figure S16). LCC2/cc-pVDZ vertical excitation energies of the studied azo-linked BODIPY dimers compared to the therapeutic window (Figure S17). Optimized M06-2X/cc-pVDZ T1 geometries of the structures shown in Table 4 of the main text (Figure S18). Acknowledgments We thank the Natural Sciences and Engineering Research Council (NSERC) of Canada for financial support and the Canadian Foundation for Innovation (New Opportunities Fund) for support for computational infrastructure. This research has been enabled by the use of computing resources provided by WestGrid and Compute/Calcul Canada.

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